CN106757046A - A kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit and preparation method thereof - Google Patents
A kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit and preparation method thereof Download PDFInfo
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- CN106757046A CN106757046A CN201611246473.5A CN201611246473A CN106757046A CN 106757046 A CN106757046 A CN 106757046A CN 201611246473 A CN201611246473 A CN 201611246473A CN 106757046 A CN106757046 A CN 106757046A
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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
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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Abstract
The invention discloses a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit and preparation method thereof, in terms of mass fraction, its preparing raw material includes：35~50 parts of intermediate products, 3.2~4.8 parts of thiocarbamides, 1.2~2.4 parts of nitranols, 1.2~2.4 parts of sulfurous acid and 40~60 parts of water, the preparing raw material of the intermediate product includes laurate and TEPA, and the mass ratio of laurate and TEPA is 1：(1~2).Corrosion inhibiter prepared by the present invention has consumption small, and the term of validity is long, low cost and other advantages, and applying can effectively control pipeline corrosion in actual production, it is ensured that safety in production.
Description
Technical field
The invention belongs to the metallic material corrosion in natural gas well surface duct internal corrosion environment and protection field, specifically relate to
And a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit and preparation method thereof.
Background technology
The corrodible property of Changqing Gas Fields ground gas transmission line is micro- containing H2S, low carbonated, there is different dense in output water
The HCO of degree3 -、Cl-Ion etc., and corrosive medium pH value change greatly.The surface line for being served in the corrosive environment uses 20#
Ordinary carbon steel, part pipeline corrosion is relatively serious, needs filling corrosion inhibiter to carry out control pipeline internal corrosion in production process.
The corrosion inhibiter research of anti-natural gas surface line corrosion is relatively fewer at present, anti-for natural gas conveying pipeline inner wall
Rotten corrosion inhibiter is main based on oil soluble corrosion inhibiter, and preferably, proportion is generally 0.85~0.98g/ to such corrosion inhibiter absorption film-forming
cm3, it is adaptable to it is simple high containing CO2The corrosive environment of corrosion, the inhibition effect in the case where pipeline hydrops water content and liquid level are all higher
It is really poor, it is limited for corrosive environment protecting effect at High water cut high salinity pipeline hydrops.So, targetedly develop and be applicable
In sulfur-bearing moisture delivery pipe to corrosion inhibiter have great significance.
The content of the invention
It is an object of the invention to provide a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit and preparation method thereof, with gram
The defect that above-mentioned prior art is present is taken, corrosion inhibiter prepared by the present invention has consumption small, and the term of validity is long, low cost and other advantages,
Applying can effectively control pipeline corrosion in actual production, it is ensured that safety in production.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, in terms of mass fraction, its preparing raw material includes：35~50 parts
Intermediate product, 3.2~4.8 parts of thiocarbamides, 1.2~2.4 parts of nitranols, 1.2~2.4 parts of sulfurous acid and 40~60 parts
Water, the preparing raw material of the intermediate product includes laurate and TEPA, and laurate and TEPA mass ratio
It is 1：(1~2).
Further, in terms of mass fraction, its preparing raw material includes：42 parts of intermediate products, 4 parts of thiocarbamides, 2 parts of tricresyl phosphate second
Hydramine, 2 parts of sulfurous acid and 50 parts of water, the preparing raw material of the intermediate product include laurate and TEPA, and bay
The mass ratio of acid and TEPA is 1：1.1.
Further, the preparation method of the intermediate product is：Carried out after laurate, TEPA are added into reactor
Distillation reaction, then catalytic reaction is carried out as catalyst using sodium chloroacetate/alkali, it is cooled to room temperature and obtains final product intermediate product.
Further, described distillation reaction is specially：3h is reacted at 150 ± 5 DEG C, 230 DEG C of reactions are then heated to
2h。
Further, described catalytic reaction is specially：1~1.5h of stirring reaction under the conditions of 180 ± 5 DEG C.
Further, it is 3.5-6.5, H that the corrosion inhibiter is applied to pH value2S Han Liang≤100mg/m3、CO2Han Liang≤1%,
Corrosive environment of the salinity in 50~100g/L.
A kind of preparation method of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, comprises the following steps：
Step one：By laurate and TEPA according to 1：The mass ratio of (1~2) carries out distilling anti-after adding reactor
Should, then catalytic reaction is carried out as catalyst using sodium chloroacetate/alkali, it is subsequently cooled to room temperature and obtains final product intermediate product；
Step 2：35~50 parts of intermediate products and 3.2~4.8 parts of thiocarbamides are reacted at a temperature of 150 ± 5 DEG C, is added
1.2~2.4 parts of nitranols and 1.2~2.4 parts of sulfurous acid phosphatization 1-2h, are then cooled to 50 ± 5 DEG C, add 40~60
Part water dissolves are simultaneously cooled to the corrosion inhibiter that room temperature obtains for sulfur-bearing moisture conveyance conduit.
Further, distillation reaction is specially in step one：3h is reacted at 150 ± 5 DEG C, 230 DEG C is then heated to instead
Answer 2h.
Further, catalytic reaction is specially in step one：1~1.5h of stirring reaction under the conditions of 180 ± 5 DEG C.
Further, it is 3.5-6.5, H that prepared corrosion inhibiter is applied to pH value2S Han Liang≤100mg/m3、CO2Han Liang≤
1%th, corrosive environment of the salinity in 50~100g/L.
Compared with prior art, the present invention has following beneficial technique effect：
Corrosion inhibiter of the invention is a kind of water miscible chemical agent, and proportion is 1.02g/cm3Left and right, produces in high salinity
Corrosion mitigating effect is good in the case that water and liquid level are all high.It is low containing H in moisture conveyance conduit2S (﹤ 100mg/m3), it is low containing CO2
Under (﹤ 1%), the corrosive environment of concentrated water (50~100g/L), chemical feeding quantity is 30~50ppm, and electrochemistry corrosion inhibition rate exists
More than 85%, weightless corrosion inhibition rate corrosion rate more than 80% or definitely is less than professional standard value 0.076mm/a, corrosion inhibiter tool
There is consumption small, the term of validity is long, low cost and other advantages, applying can effectively control pipeline corrosion in actual production, it is ensured that safety is raw
Produce.
The inventive method makes itself and Fe by introducing hybridized atom sulphur and phosphorous polar group2+Complexing changes into insoluble
The iron sulfide diaphragm of property；Using cycloalkyl space arrangement entirety, the characteristics of the excellent adsorption of metal surface, it is designed with many absorption
The imidazolidine derivatives corrosion inhibiter host compound of the heart, increases its protected area, reduces inhibiter consumption；Phosphorous are added simultaneously
Acid, the water-soluble and dispersiveness of Sulphur-containing Imidazole quinoline is improved using phosphatization method of modifying；In addition, adding a small amount of tricresyl phosphate ethanol
Amine, further strengthens the synergy between alcohol amine groups and phosphate radical, because its side chain is very more, has certainly when film is damaged
The ability of reparation, the synergy of the condensate/crude oil for finally being contained using natural gas line in itself realizes the width of corrosion inhibiter
Adaptability and efficient requirement.
Brief description of the drawings
Fig. 1 is corrosion coupon microscopic appearance before addition corrosion inhibiter of the present invention；
Fig. 2 is addition corrosion inhibiter post-etching lacing film microscopic appearance of the present invention.
Specific embodiment
Embodiments of the present invention are described in further detail below：
A kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, in terms of mass fraction, its preparing raw material includes：35~50 parts
Intermediate product, 3.2~4.8 parts of thiocarbamides, 1.2~2.4 parts of nitranols, 1.2~2.4 parts of sulfurous acid and 40~60 parts
Water, the preparing raw material of the intermediate product includes laurate and TEPA, and laurate and TEPA mass ratio
It is 1：(1~2), more optimizes, and its preparing raw material includes：42 parts of intermediate products, 4 parts of thiocarbamides, 2 parts of nitranols, 2 parts of Asias
Sulfuric acid and 50 parts of water, the preparing raw material of the intermediate product include laurate and TEPA, and laurate and four ethene
The mass ratio of five amine is 1：1.1.
The preparation method of intermediate product is：By laurate, TEPA reaction mass add reactor after 150 ± 5
3h is reacted at DEG C, 230 DEG C of reaction 2h is then heated to, then using sodium chloroacetate/alkali as catalyst, stirred under the conditions of 180 ± 5 DEG C
Mixing carries out 1~1.5h of catalytic reaction, is cooled to room temperature and obtains final product intermediate product.
A kind of preparation method of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, comprises the following steps：
Step one：By laurate and TEPA according to 1：At 150 ± 5 DEG C after the mass ratio addition reactor of (1~2)
Lower reaction 3h, then heats to 230 DEG C of reaction 2h, then using sodium chloroacetate/alkali as catalyst, stirred under the conditions of 180 ± 5 DEG C
1~1.5h of catalytic reaction is carried out, room temperature is subsequently cooled to and is obtained final product intermediate product；
Step 2：35~50 parts of intermediate products and 3.2~4.8 parts of thiocarbamides are reacted at a temperature of 150 ± 5 DEG C, is added
1.2~2.4 parts of nitranols and 1.2~2.4 parts of sulfurous acid phosphatization 1-2h, are then cooled to 50 ± 5 DEG C, add 40~60
Part water dissolves are simultaneously cooled to the corrosion inhibiter that room temperature obtains for sulfur-bearing moisture conveyance conduit.
It is 3.5-6.5, H that the corrosion inhibiter that the present invention is provided is applied to pH value2S Han Liang≤100mg/m3、CO2Han Liang≤1%,
Corrosive environment of the salinity in 50~100g/L.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
On the there-necked flask for installing water knockout drum, reflux condensing tube and agitator, by 1：1.05 mass ratio by laurate,
After TEPA reaction mass adds reactor, 3h is reacted at (150 ± 5) DEG C, be brought rapidly up to 230 DEG C being reacted
2h, constantly has water to distillate in course of reaction, after high temperature dehydration, then using sodium chloroacetate/alkali as catalyst, in 180 ± 5 DEG C of conditions
Lower stirring carries out catalytic reaction 1h, is cooled to room temperature and obtains intermediate product.
Mass parts are respectively 35 parts of intermediate products and 4.8 parts of thiocarbamides in (150 ± 5) DEG C reaction 3h, 2.4 parts are subsequently to added into
Nitranol and 1.2 parts of phosphorous acid phosphatization 1h, after be cooled to during (50 ± 5) DEG C add 60 parts of water and fully dissolve, cool down
Imidazoline sulphur phosphor corrosion inhibitor is obtained to normal temperature.The influence of condensate is simulated using normal octane, in corrosive medium (50mg/m3H2S、
0.5%CO2, 60g/L CaCl2) middle addition 30ppm imidazoline sulphur phosphor corrosion inhibitors, the normal octane of liquid quality fraction 1% is added,
Add before and after normal octane, electrochemistry corrosion inhibition rate brings up to 87.8% by 76.9%, compound the lifting of 1% normal octane corrosion mitigating effect,
Show that the corrosion inhibiter can produce good cooperative effect with gas well condensate.
Embodiment 2
On the there-necked flask for installing water knockout drum, reflux condensing tube and agitator, by 1：1.2 mass ratio is by bay
After acid, TEPA reaction mass add reactor, 4h is reacted at (150 ± 5) DEG C, be brought rapidly up to 230 DEG C carrying out anti-
2h is answered, constantly there is water to distillate in course of reaction, after high temperature dehydration, then using sodium chloroacetate/alkali as catalyst, in 180 ± 5 DEG C of bars
Stirring carries out catalytic reaction 1.5h under part, is cooled to room temperature and obtains intermediate product.
Mass parts are respectively 50 parts of intermediate products and 3.2 parts of thiocarbamides in (150 ± 5) DEG C reaction 4h, 1.2 parts are subsequently to added into
Nitranol and 2.4 parts of phosphorous acid phosphatization 2h, after be cooled to during (50 ± 5) DEG C add 40 parts of water and fully dissolve, lower the temperature
Fully dissolved in the water that 50 parts are added after to (50 ± 5) DEG C, be cooled to normal temperature and obtain imidazoline sulphur phosphor corrosion inhibitor.Using normal octane
The influence of condensate is simulated, in corrosive medium (50mg/m3H2S, 0.5%CO2, 60g/L CaCl2) middle addition 30ppm imidazolines
Sulphur phosphor corrosion inhibitor, adds the normal octane of liquid quality fraction 1%, adds before and after normal octane, and electrochemistry corrosion inhibition rate is carried by 79.2%
It is high to compound the lifting of 1% normal octane corrosion mitigating effect to 89.8%, show that the corrosion inhibiter can produce good association with gas well condensate
Same effect.
Embodiment 3
On the there-necked flask for installing water knockout drum, reflux condensing tube and agitator, by 1：1.1 mass ratio is by bay
After acid, TEPA reaction mass add reactor, 5h is reacted at (150 ± 5) DEG C, be brought rapidly up to 230 DEG C carrying out anti-
2h is answered, constantly there is water to distillate in course of reaction, after high temperature dehydration, then using sodium chloroacetate/alkali as catalyst, in 180 ± 5 DEG C of bars
Stirring carries out catalytic reaction 1.2h under part, is cooled to room temperature and obtains intermediate product.
Mass parts are respectively 42 parts of intermediate products and 4 parts of thiocarbamides in (150 ± 5) DEG C reaction 2h, 2 parts of phosphoric acid are subsequently to added into
Triethanolamine and 2 parts of phosphorous acid phosphatization 1.5h, after be cooled to during (50 ± 5) DEG C add 50 parts of water and fully dissolve, be cooled to often
Temperature obtains imidazoline sulphur phosphor corrosion inhibitor.The influence of condensate is simulated using normal octane, in corrosive medium (50mg/m3H2S, 0.5%
CO2, 60g/L CaCl2) middle addition 30ppm imidazoline sulphur phosphor corrosion inhibitors, the normal octane of liquid quality fraction 1% is added, add
Before and after normal octane, electrochemistry corrosion inhibition rate brings up to 91.6% by 80.2%, compounds the lifting of 1% normal octane corrosion mitigating effect, shows
The corrosion inhibiter can produce good cooperative effect with gas well condensate.
As described above, embodiments of the invention are explained, as long as of the invention essentially without departing from
Inventive point and effect can have many deformations, and this will be readily apparent to persons skilled in the art.Therefore, it is such
Variation is also integrally incorporated within protection scope of the present invention.
Claims (10)
1. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, it is characterised in that in terms of mass fraction, its preparing raw material bag
Include：35~50 parts of intermediate products, 3.2~4.8 parts of thiocarbamides, 1.2~2.4 parts of nitranols, 1.2~2.4 parts of sulfurous acid with
And 40~60 parts of water, the preparing raw material of the intermediate product includes laurate and TEPA, and laurate and four ethene five
The mass ratio of amine is 1：(1~2).
2. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 1, it is characterised in that with mass parts
Number meter, its preparing raw material includes：42 parts of intermediate products, 4 parts of thiocarbamides, 2 parts of nitranols, 2 parts of sulfurous acid and 50 parts of water,
The preparing raw material of the intermediate product includes laurate and TEPA, and the mass ratio of laurate and TEPA is 1：
1.1。
3. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 1 and 2, it is characterised in that described
The preparation method of intermediate product is：Distillation reaction is carried out after laurate, TEPA are added into reactor, then with monoxone
Sodium/alkali carries out catalytic reaction as catalyst, is cooled to room temperature and obtains final product intermediate product.
4. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 3, it is characterised in that described steaming
Reaction is evaporated to be specially：3h is reacted at 150 ± 5 DEG C, 230 DEG C of reaction 2h are then heated to.
5. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 3, it is characterised in that described urges
Change reaction to be specially：1~1.5h of stirring reaction under the conditions of 180 ± 5 DEG C.
6. a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 1 and 2, it is characterised in that described
It is 3.5-6.5, H that corrosion inhibiter is applied to pH value2S Han Liang≤100mg/m3、CO2Han Liang≤1%, salinity are 50~100g/L's
Corrosive environment.
7. the preparation method of a kind of corrosion inhibiter for sulfur-bearing moisture conveyance conduit, it is characterised in that comprise the following steps：
Step one：By laurate and TEPA according to 1：The mass ratio of (1~2) carries out distillation reaction after adding reactor,
Catalytic reaction is carried out as catalyst using sodium chloroacetate/alkali again, room temperature is subsequently cooled to and is obtained final product intermediate product；
Step 2：35~50 parts of intermediate products and 3.2~4.8 parts of thiocarbamides are reacted at a temperature of 150 ± 5 DEG C, add 1.2~
2.4 parts of nitranols and 1.2~2.4 parts of sulfurous acid phosphatization 1-2h, are then cooled to 50 ± 5 DEG C, add 40~60 parts of water
Dissolve and be cooled to the corrosion inhibiter that room temperature obtains for sulfur-bearing moisture conveyance conduit.
8. a kind of preparation method of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 7, its feature exists
In distillation reaction is specially in step one：3h is reacted at 150 ± 5 DEG C, 230 DEG C of reaction 2h are then heated to.
9. a kind of preparation method of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 7, its feature exists
In catalytic reaction is specially in step one：1~1.5h of stirring reaction under the conditions of 180 ± 5 DEG C.
10. a kind of preparation method of corrosion inhibiter for sulfur-bearing moisture conveyance conduit according to claim 7, its feature exists
In it is 3.5-6.5, H that prepared corrosion inhibiter is applied to pH value2S Han Liang≤100mg/m3、CO2Han Liang≤1%, salinity are 50
The corrosive environment of~100g/L.
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