CN115948154B - Corrosion inhibitor and preparation method and application thereof - Google Patents
Corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- CN115948154B CN115948154B CN202211531718.4A CN202211531718A CN115948154B CN 115948154 B CN115948154 B CN 115948154B CN 202211531718 A CN202211531718 A CN 202211531718A CN 115948154 B CN115948154 B CN 115948154B
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- 238000005260 corrosion Methods 0.000 title claims abstract description 101
- 230000007797 corrosion Effects 0.000 title claims abstract description 99
- 239000003112 inhibitor Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 25
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 palmitoyl imidazoline Chemical compound 0.000 claims abstract description 25
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 claims abstract description 25
- 229940046307 sodium thioglycolate Drugs 0.000 claims abstract description 25
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 7
- 238000011161 development Methods 0.000 claims description 6
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 4
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229940083037 simethicone Drugs 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 12
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- 229910000831 Steel Inorganic materials 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004429 atom Chemical group 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 239000010779 crude oil Substances 0.000 abstract 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a corrosion inhibitor, a preparation method and application thereof, wherein the corrosion inhibitor comprises a film forming agent, and the film forming agent comprises the following components in parts by mass: 20-50 parts of palmitic acid imidazoline and 10 parts of sodium thioglycolate. According to the invention, the surfactant and the film forming agent are added into the corrosion inhibitor at the same time, and the existence of the ether nonionic surfactant reduces the surface tension of gas and liquid; sodium thioglycolate is added into the film forming agent, S atoms are contained in the sodium thioglycolate, the sodium thioglycolate can react with Fe atoms of steel to generate ferrous sulfide which is difficult to dissolve in water, the ferrous sulfide and the palmitoyl imidazoline are adsorbed on the surface of the steel to form a compact ferrous sulfide film, the surface of the steel is covered, and the corrosion is slowed down or prevented from continuously occurring. The film forming agent and the surfactant cooperate to enable the corrosion inhibitor to enable the oil-water interfacial tension of the water phase to be not higher than 2.83mN/m under the high temperature condition of 180 ℃, the average corrosion speed to be not higher than 0.078mm/a, and the corrosion inhibitor has excellent surface tension reduction and corrosion inhibition performance and ensures the crude oil yield of an oil well.
Description
Technical Field
The invention relates to the field of corrosion and protection, in particular to a corrosion inhibitor and a preparation method and application thereof.
Background
The development of oil and gas fields is an important link of the petroleum industry, plays a role in the petroleum industry, and along with the development of petroleum exploration technology, more and more oil and gas field development is gradually turned to the exploitation condition of a high-temperature deep well. The high temperature and high pressure downhole conditions make it important to slow the corrosion rate of the special environment to the well and tools to ensure the normal operating conditions of the well. However, the pressure coefficient of the general stratum is higher in the high-temperature deep well environment, the phenomenon that water phase stays in a porous medium can occur in the drilling, completion, repair and exploitation operation processes, water saturation in a near-well zone can be increased after water is immersed into an oil layer, permeability of the high-temperature deep well is reduced, water lock damage is generated, and corrosion to downhole tubular tools is aggravated.
At present, a high-density well completion fluid and a well repair fluid mainly adopt some solid-free high-density clean brine, and in order to reduce the water lock damage of a hypotonic reservoir, the well completion fluid or the well repair fluid must have lower surface tension; meanwhile, as the high-density clean brine has strong corrosiveness to metals at high temperature, in order to control corrosion of well completion fluid and well repair fluid to pipes and tools at high temperature in the pit, the well completion fluid and the well repair fluid are required to have high-temperature corrosion inhibition performance.
The corrosion inhibitor added in the well completion fluid or the well repair fluid in the prior art has relatively poor temperature resistance, and can not effectively control corrosion of the well completion fluid or the well repair fluid to pipes and tools under the underground high-temperature condition in the working environment of a high-temperature deep well in oil-gas field exploitation. At present, by independently adding a surfactant into a well completion fluid and a well repair fluid, the technical aim of reducing the gas-liquid phase surface tension of the well completion fluid and the well repair fluid is fulfilled; the technical aim of reducing the corrosion of the completion fluid or the workover fluid to the underground pipe is achieved by independently adding the corrosion inhibitor into the completion fluid or the workover fluid. The reason why the surfactant or the corrosion inhibitor is added separately according to the function of the treating agent in the prior art is that the corrosion inhibitor and the surfactant are not compatible with each other when added simultaneously, so that the treating agent with good corrosion inhibition effect has poor capability of reducing the surface tension, and the treating agent with strong surface tension has almost no corrosion inhibition capability. The prior art fails to form a treating agent which can reduce the surface tension and has good corrosion control capability.
Disclosure of Invention
The invention provides a film forming agent, which is used as an additive of well completion fluid or well completion fluid, and can be matched with a conventional surfactant to enable the well completion fluid or well completion fluid to achieve the purposes of reducing the surface tension and effectively inhibiting corrosion on underground pipes and tools under the conditions of high temperature and high pressure.
It is another object of the present invention to provide a corrosion inhibitor.
It is another object of the present invention to provide a corrosion inhibitor for use in oil and gas field development.
In order to solve the technical problems, the invention adopts the following technical scheme:
The film forming agent comprises the following components in parts by mass:
20-50 parts of palmitoyl imidazoline;
10 parts of sodium thioglycolate.
The composition of the film forming agent comprises palmitic acid imidazoline and sodium thioglycolate, wherein the sodium thioglycolate contains S atoms and can react with Fe atoms in steel to generate ferrous sulfide which is difficult to dissolve in water, palmitic acid imidazoline molecules are adsorbed on the generated ferrous sulfide to form a compact ferrous sulfide film, and a compact and stable protective film is formed on the surface of the steel by adsorption, so that corrosion can be effectively slowed down or prevented from continuously occurring.
Preferably, the film forming agent comprises the following components in parts by mass: 30-40 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
The film forming agent provided by the invention has the advantages that the film forming effect is poor and the corrosion rate is high due to the fact that the content of sodium thioglycolate is too low.
The palmitoyl imidazoline in the film forming agent is prepared by the following steps:
The palmitic acid, tetraethylenepentamine, dimethylbenzene and boric acid are added into a reaction kettle according to the mass ratio of 100:30-50:0.1-0.2, and are heated to 130-200 ℃ for 2-4 hours at first time, heated to 200-250 ℃ for 3-5 hours at second time, and naturally cooled to obtain the palmitic acid-based imidazoline.
Preferably, in the preparation method of the palmitic acid-based imidazoline in the film forming agent, the mass ratio of palmitic acid, tetraethylenepentamine, xylene and boric acid is 100 (90-95) (40-45) (0.01-0.03).
The content ratio of each component in the preparation method of the palmitic acid-based imidazoline in the film-forming agent also influences the specific surface area reduction and corrosion inhibition effect of the obtained corrosion inhibitor on a system, and when the mass ratio of palmitic acid, tetraethylenepentamine, dimethylbenzene and boric acid in the prepared palmitic acid-based imidazoline is 100:95:40:0.03, the corrosion inhibition effect of the film-forming agent obtained by compounding the generated palmitic acid-based imidazoline with sodium thioglycolate is the best.
Preferably, in the preparation method of the palmitic acid-based imidazoline in the film forming agent, the primary heating temperature is 160-180 ℃ and the reflux time is 3 hours.
In the preparation method of the palmitic acid-based imidazoline in the film forming agent, the primary heating temperature is too high, so that an amide intermediate product is not sufficiently formed, the product is directly cyclized, the content of the final product palmitic acid-based imidazoline is reduced, the content of the amide intermediate product is lower due to the fact that the heating temperature is too low, and the content of the final product palmitic acid-based imidazoline is also lower. Too long a reflux time results in consumption of starting materials and amide intermediates, reduced levels of final products, and too short a reflux time results in lower levels of amide intermediates formed, and reduced levels of final products.
Preferably, in the preparation method of the palmitic acid-based imidazoline in the film forming agent, the secondary heating temperature is 220-240 ℃ and the reflux time is 4 hours.
In the preparation method of the palmitoyl imidazoline in the film forming agent, the excessive high secondary heating temperature can lead to the formation of five-membered ring type imidazoline ring opening, the corrosion inhibition capability is poor, and the excessive low heating temperature can lead to the formation of five-membered ring type imidazoline ring forming difficulty and the corrosion inhibition capability is poor. The excessive backflow time can lead to the reduction of the effective content of the formed five-membered ring type imidazoline to cause the waste of materials, the excessive backflow time can lead to the failure of the complete evaporation of the water serving as a reaction byproduct, and the reduction of the effective content of the formed five-membered ring type imidazoline can lead to the deterioration of corrosion inhibition capability.
The invention also protects a corrosion inhibitor, which comprises the following components in parts by mass:
100 parts of water;
45-60 parts of the film forming agent;
30-40 parts of a surfactant;
5-10 parts of defoaming agent;
the surfactant is an ether nonionic surfactant; the defoaming agent is one or two of an ether defoaming agent and an organic silicon defoaming agent.
The surfactant is one or two selected from perfluorooctyl polyoxyethylene ether and alkylphenol polyoxyethylene ether.
The ether nonionic surfactant can exist stably at 180-200 ℃, can obviously reduce the surface tension of a system, and can be used for preparing a corrosion inhibitor through synergistic action with a film forming agent, and the corrosion inhibitor has the performance of obviously reducing the surface tension and corrosion rate of the system at the same time under a high-temperature environment.
The defoamer is one or two selected from laureth and simethicone.
The laureth can effectively inhibit the generation of bubbles in the system under the high temperature condition, the surface tension of the dimethyl silicone oil is small, and the surface tension of the dimethyl silicone oil can not be increased in the process of eliminating the bubbles in the system.
The film forming agent, the ether nonionic surfactant and the defoamer are prepared into the corrosion inhibitor, wherein the nonionic surfactant has the capability of reducing the system surface tension at a high temperature of 180-200 ℃ and the film forming agent is synergistically enhanced, so that the corrosion inhibitor has the functions of reducing the surface tension and inhibiting corrosion at a high temperature.
The preparation method of the corrosion inhibitor comprises the following steps:
And sequentially adding the corrosion inhibitor, the surfactant and the defoamer into water according to the composition proportion of each component under the stirring condition, and stirring uniformly to obtain the corrosion inhibitor.
The stirring speeds of the stirring device are all set to 800-1000 rpm.
The invention also protects application of the corrosion inhibitor in oil and gas field development.
Compared with the prior art, the invention has the beneficial effects that:
The invention adds the surface active agent and the film forming agent into the corrosion inhibitor, the ether nonionic surface active agent can exist stably at the high temperature of 180-200 ℃, the gas-liquid surface tension and the oil-water interfacial tension are obviously reduced, and the corrosion inhibitor prepared by the synergistic effect with the film forming agent has the property of obviously reducing the system surface tension and the corrosion rate at the high temperature of 180-200 ℃. The oil-water interfacial tension of the corrosion inhibitor is not higher than 2.83mN/m at the high temperature of 180 ℃, the corrosion inhibitor is added into the well repairing liquid, 13Cr steel is placed for 15 days at the high temperature of 180 ℃, the average corrosion speed of the 13Cr steel is not higher than 0.078mm/a, and the corrosion inhibitor has excellent surface tension reduction and corrosion inhibition performances.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Alterations, substitutions, and modifications will remain within the scope of the invention for those skilled in the art upon understanding the invention. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The raw material sources are as follows: the reagents used in the examples and comparative examples of the present application were commercially available.
Example 1
A film forming agent consists of the following components in parts by mass:
30 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
The preparation method of the palmitic acid-based imidazoline in the film forming agent comprises the following steps:
Palmitic acid, tetraethylenepentamine, dimethylbenzene and boric acid are added into a reaction kettle according to the mass ratio of 100:95:40:0.03, the mixture is heated at 160 ℃ for reaction reflux for 3 hours, heated at 220 ℃ for reaction reflux for 4 hours, and naturally cooled to obtain the palmitic acid-based imidazoline.
Examples 2 to 7
A film forming agent consists of the following components in parts by mass:
30 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
The difference from example 1 is that the preparation methods of the palmitoyl imidazolines of examples 2 to 7 are different, the specific differences are shown in Table 1
TABLE 1 parameters of the preparation method of palmitoyl imidazoline
Note that: the raw material ratio shown in Table 1 refers to the mass ratio of palmitic acid, tetraethylenepentamine, xylene and boric acid
Example 8
A film forming agent consists of the following components in parts by mass:
20 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
Wherein the preparation method of palmitoyl imidazoline is the same as in example 1.
Example 9
A film forming agent consists of the following components in parts by mass:
50 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
Wherein the preparation method of palmitoyl imidazoline is the same as in example 1.
Example 10
A film forming agent consists of the following components in parts by mass:
40 parts of palmitoyl imidazoline; 10 parts of sodium thioglycolate.
Wherein the preparation method of palmitoyl imidazoline is the same as in example 1.
Examples 11 to 20
The corrosion inhibitor consists of the following components in parts by mass:
100 parts of water, 50 parts of film forming agent, 35 parts of perfluoro octyl polyoxyethylene ether surfactant and 10 parts of laureth.
A method for preparing a corrosion inhibitor, comprising the following steps:
Pouring 100 parts of water into a stainless steel high-stirring cup, placing on a high-speed stirrer at 800rpm, adding 50 parts of film forming agent, continuously stirring for 10min, adding 35 parts of perfluorooctyl polyoxyethylene ether surfactant, stirring for 5min, adding 10 parts of laureth, and continuously stirring for 3min to obtain the corrosion inhibitor;
The film forming agents added in the process of preparing the sustained release agent in the embodiments 11 to 20 correspond to the film forming agents provided in the embodiments 1 to 10 in sequence.
Example 21
The difference from example 11 is that the corrosion inhibitor consists of the following components in parts by mass: 100 parts of water and 45 parts of film forming agent; 30 parts of alkylphenol polyoxyethylene ether; 5 parts of dimethyl silicone oil.
Example 22
The difference from example 11 is that the corrosion inhibitor consists of the following components in parts by mass: 100 parts of water and 60 parts of film forming agent; 40 parts of alkylphenol polyoxyethylene ether; 5 parts of laureth.
Comparative example 1
The difference from example 11 is that only palmitoyl imidazoline is added to the film forming agent, and sodium thioglycolate is not added for compounding.
Comparative example 2
The difference from example 11 is that the corrosion inhibitor consists of the following mass components: 100 parts of water; 35 parts of a surfactant; 10 parts of defoaming agent.
Comparative example 3
The difference from example 11 is that the film forming agent consists of the following components in parts by mass: 50 parts of palmitoyl imidazoline and 50 parts of sodium thioglycolate.
Comparative example 4
The difference from example 11 is that the film forming agent consists of 70 parts by mass of palmitoyl imidazoline and 10 parts by mass of sodium thioglycolate.
Performance testing
The corrosion inhibitors obtained in examples 11 to 22 and comparative examples 1 to 4 were subjected to surface tension and corrosion inhibition performance tests:
the method for measuring the gas-liquid surface tension comprises the following steps:
(1) Distilled water and kerosene are mixed according to a ratio of 1:1, and 2 weight percent of sample is added into the distilled water, wherein the sample is the corrosion inhibitor prepared in examples 11-22 and comparative examples 1-4, and the mixture is fully and uniformly mixed;
(2) The JZ-200W surface tension tester is adopted to measure the gas-liquid surface tension by a platinum loop method according to the oil and gas industry standard SY/T5310-1999 surface and interfacial tension measuring method, and the unit is: mN/m.
The surface tension data of the tested examples 11-13, 21-22 and comparative examples 1-3 are shown in Table 2.
Table 2 results of gas-liquid surface tension test of Corrosion inhibitors prepared in examples 11 to 13, 21 to 22 and comparative examples 1 to 3
As can be seen from table 2: the corrosion inhibitors prepared in examples 11-13 and 21-22 can reduce the gas-liquid surface tension of the water phase from 69.86mN/m to 23.69mN/m at least at normal temperature, and the oil-water interfacial tension from 22.64mN/m to 2.16mN/m; the system added with the corrosion inhibitor can lead the surface tension of the gas-liquid surface tension of the system to be not higher than 27.54mN/m and the interfacial tension of oil-water to be not higher than 2.83mN/m under the high-temperature environment of 180 ℃. The corrosion inhibitor obtained in the example is superior to that in the example 12 in terms of the reduction of the system surface tension. Comparative example 2 with only surfactant and no film former, the gas-liquid surface tension of the system at room temperature was 32.65mN/m, and the oil-water interfacial tension was 3.75mN/m; the gas-liquid surface tension of the system is 33.98mN/m and the oil-water interfacial tension is 3.91mN/m under the high temperature environment of 180 ℃. In addition, compared with the film forming agent 2, the film forming agent obtained in the comparative examples 1,3 and 4 has the effect of reducing the surface tension of the system due to the range of the added sodium thioglycolate. In conclusion, the synergistic effect of the film forming agent and the surfactant added simultaneously in the corrosion inhibitor obtained in the example is more remarkable in reducing the surface tension of the system compared with the corrosion inhibitor obtained in the comparative example.
Corrosion rate test:
(1) The density of water is adjusted to 1.55g/cm 3 by adopting potassium formate;
(2) Adding 2wt% of sample into 1.55g/cm 3 potassium formate solution, wherein the samples are prepared by fully and uniformly mixing corrosion inhibitors prepared in examples 11-22 and comparative examples 1-4;
(3) The corrosion rate of the metal is measured according to the quality difference of the metal test pieces before and after corrosion by adopting a hanging piece weightlessness method according to the standard SY/T5329-94 of the oil and gas industry of China, namely the water quality recommendation index and analysis method of clastic rock oil deposit, and the obtained corrosion rate data are shown in Table 2. The etching condition is 180 ℃ for 15d.
(4) The average corrosion rate calculation formula:
Wherein v a -corrosion rate, mm/a; Δw—test piece weight loss, g; s, the corrosion area of a test piece, cm 2; t-corrosion time, h; ρ—test piece material density, g/cm 3; c-unit conversion constant, 8.76X10 4.
TABLE 3 Corrosion inhibitor Corrosion resistance prepared in examples 11-22 and comparative examples 1-4
As can be seen from Table 3, the corrosion inhibitor of example 11 was free of sodium thioglycolate and the corrosion inhibitor of comparative example 3 was free of film forming agent, compared with comparative examples 1 and 2, and the corrosion rates of the corrosion inhibitor of example 11 and comparative examples 1 and 2 for 13Cr were increased rapidly from 0.049mm/a to 0.1025mm/a and 0.2214mm/a, respectively, under the same conditions. It can be seen that the slow release effect of the corrosion inhibitor is rapidly reduced by adding no film forming agent or sodium thioglycolate.
Example 11 in comparison with examples 16,17, the primary heating temperature and reflux time in the process for preparing palmitoyl imidazoline in the film formers of examples 11 and 16,17, respectively, were: 160 ℃,3h,130 ℃,4h,200 ℃ and 3h; the secondary heating temperature and the reflow time are respectively as follows: 220 ℃,4h,250 ℃,5h,200 ℃ and 4h. The corrosion rates of the corrosion inhibitor added into the well repairing liquid for 13Cr are respectively increased from 0.049mm/a to 0.078mm/a and 0.074mm/a. It can be seen that the heating temperature in the method for preparing the palmitic acid-based imidazoline in the film forming agent is high and low, and the reflux time can influence the slow release effect of the corrosion inhibitor. This is because an excessively high primary heating temperature results in insufficient formation of the amide intermediate product, direct cyclization, and an excessively low heating temperature results in a low amide intermediate product. The excessive heating temperature can lead to the formation of five-membered ring type imidazoline ring opening, the excessive heating temperature can lead to the formation of five-membered ring type imidazoline ring forming difficulty, and the factors can lead to the reduction of the effective content of the five-membered ring type imidazoline in the final product, so that the corrosion inhibition capability of the corrosion inhibitor is poor.
Example 11 in comparison with comparative examples 3 and 4, the mass ratio of the palmitoyl imidazoline to the sodium thioglycolate in the film forming agent in the corrosion inhibitors prepared in example 11 and comparative examples 3 and 4 is 3:1,1:1 and 7:1 respectively, and the corrosion rates of the corrosion inhibitors added into the well servicing fluid for 13Cr are increased to 0.080mm/a and 0.083mm/a from 0.049mm/a respectively. It can be seen that too high or too low an amount of sodium thioglycolate added affects the slow release effect of the corrosion inhibitor. The data in Table 2 are combined to prove that the corrosion inhibitors prepared in examples 11-22 can obviously reduce the corrosion rate of a system while reducing the surface tension of gas and liquid when being applied to well servicing fluid under the synergistic effect of a film forming agent and a surfactant.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The film forming agent is characterized by comprising the following components in parts by mass:
20-50 parts of palmitoyl imidazoline;
Sodium thioglycolate 10 parts
The palmitoyl imidazoline is prepared through the following steps:
The palmitic acid, tetraethylenepentamine, dimethylbenzene and boric acid are added into a reaction kettle according to the mass ratio of 100:30-50:0.1-0.2, and are heated to 130-200 ℃ for 2-4 hours at first time, heated to 200-250 ℃ for 3-5 hours at second time, and naturally cooled to obtain the palmitic acid-based imidazoline.
2. The film forming agent according to claim 1, which comprises the following components in parts by mass:
30-40 parts of palmitoyl imidazoline;
10 parts of sodium thioglycolate.
3. The film forming agent according to claim 1, wherein the mass ratio of palmitic acid, tetraethylenepentamine, xylene and boric acid in the preparation method of the palmitic acid-based imidazoline is 100 (90-95): 40-45): 0.01-0.03.
4. The film forming agent according to claim 1, wherein the primary heating temperature in the preparation method of the palmitoyl imidazoline is 160-180 ℃ and the reflux time is 3h.
5. The film forming agent according to claim 1, wherein the secondary heating temperature in the preparation method of the palmitoyl imidazoline is 220-240 ℃ and the reflux time is 4 hours.
6. The corrosion inhibitor is characterized by comprising the following components in parts by mass:
100 parts of water;
45-60 parts of film forming agent according to claim 1 or 2;
30-40 parts of a surfactant;
5-10 parts of defoaming agent;
the surfactant is an ether nonionic surfactant; the defoaming agent is one or two of an ether defoaming agent and an organic silicon defoaming agent.
7. The corrosion inhibitor according to claim 6, wherein the surfactant is one or both selected from perfluorooctyl polyoxyethylene ether and alkylphenol polyoxyethylene ether.
8. The corrosion inhibitor according to claim 6, wherein the defoamer is one or two selected from the group consisting of laureth and simethicone.
9. Use of a corrosion inhibitor according to any one of claims 6 to 8 in oil and gas field development.
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