A pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion and a preparation method thereof

Abstract

The present application relates to the technical field of corrosion inhibitor, and proposes a pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion and a preparation method thereof.The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion comprises the following components in parts by mass: pyridine quaternary ammonium salt 25-35 parts, mercaptan 15-25 parts, fatty alcohol polyoxyethylene ether 3-8 parts, and solvent 40-50 parts.The preparation method of the pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion comprises the following steps: uniformly mixing the components in parts by mass to obtain the pyridine quaternary ammonium salt corrosion inhibitor.Through the above technical solution, the problem of poor corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor in the prior art is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of corrosion inhibitors, in particular to a pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion and a preparation method thereof. BACKGROUND

[0002] In addition to oil and natural gas, water, hydrogen sulfide, carbon dioxide and the like are also entrained in oil and gas fields. Dry carbon dioxide and hydrogen sulfide are not corrosive, but once dissolved in water, hydrogen ions are released, which can easily corrode steel.

[0003] Corrosion inhibitors can prevent carbon dioxide, hydrogen sulfide and the like from corroding equipment in oil and natural gas exploration. At present, the most widely used corrosion inhibitor in the oil and gas industry is a long hydrocarbon chain nitrogen-containing corrosion inhibitor. With increasingly stringent environmental requirements for corrosion inhibitors, low-toxicity, safe pyridine quaternary ammonium salt corrosion inhibitors stand out from numerous corrosion inhibitors, but the corrosion inhibition effect needs to be further improved. SUMMARY

[0004] The present application provides a pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion and a preparation method thereof, which solves the problem of poor corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor in the related art.

[0005] The technical solution of the present application is as follows:

[0006] A pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion comprises the following components in parts by mass: pyridine quaternary ammonium salt 25-35 parts, mercaptan 15-25 parts, fatty alcohol polyoxyethylene ether 3-8 parts, and solvent 40-50 parts.

[0007] As a further technical solution, the mass ratio of the pyridine quaternary ammonium salt to the mercaptan is 3:2.

[0008] As a further technical solution, the mercaptan comprises branched mercaptan 7-15 parts and unbranched mercaptan 5-13 parts.

[0009] As a further technical solution, the mass ratio of the branched mercaptan to the unbranched mercaptan is 9:11-13:7.

[0010] As a further technical solution, the mass ratio of the branched mercaptan to the unbranched mercaptan is 11:9.

[0011] As a further technical solution, the branched mercaptan has 10-14 carbon atoms.

[0012] As a further technical solution, the branched mercaptan is tert-tetradecyl mercaptan.

[0013] As a further technical solution, the unbranched mercaptan has 8-12 carbon atoms.

[0014] As a further technical solution, the branched-chain-free mercaptan is 1-decanethiol.

[0015] The application further provides a preparation method of the pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion.

[0016] As a further technical solution, the temperature of the mixing is 40-50 DEG C, and the mixing time is 50-100 min.

[0017] The working principle and beneficial effects of the application are as follows:

[0018] 1. The pyridine quaternary ammonium salt and mercaptan are used in combination, so that the corrosion inhibition rate of the pyridine quaternary ammonium salt corrosion inhibitor is improved, the problem of poor corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor in the prior art is solved, and the purpose of improving the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor is achieved.

[0019] 2. The mercaptan is further adjusted to contain branched-chain mercaptan and branched-chain-free mercaptan, so that the shielding area and adsorption are better guaranteed, and the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor is further improved.

[0020] 3. The number of carbons in the branched-chain mercaptan is optimized to 10-14, and the number of carbons in the branched-chain-free mercaptan is optimized to 8-12, so that a more compact shielding system is formed, and the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor is further improved. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor also fall within the protection scope of the application.

[0022] In the following examples and comparative examples, the pyridine quaternary ammonium salt is PBC-80, the active content is 78-82 wt%, the density (20 DEG C) is 1.03-1.08 g / cm 3 , the pH value (1 wt% aqueous solution) is 4.0-5.5, and the product is purchased from Jiuzhou Biotechnology (Suzhou) Co., Ltd.

[0023] Example 1

[0024] Pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 20 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0025] Example 2

[0026] Pyridine quaternary ammonium salt 30 parts, 1-hexanethiol 20 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0027] Example 3

[0028] Pyridine quaternary ammonium salt 35 parts, 1-hexanethiol 15 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0029] Example 4

[0030] Pyridine quaternary ammonium salt 25 parts, 1-hexanethiol 25 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0031] Example 5

[0032] Pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 7 parts, 1-hexanethiol 13 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0033] Example 6

[0034] Pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 9 parts, 1-hexanethiol 11 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0035] Example 7

[0036] Pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0037] Example 8

[0038] Pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 13 parts, 1-hexanethiol 7 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45℃ for 90min in a reaction kettle, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0039] Example 9

[0040] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, isooctyl mercaptan 15 parts, 1-hexanethiol 5 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0041] Example 10

[0042] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, 3-decanethiol 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0043] Example 11

[0044] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, tetrade c yl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0045] Example 12

[0046] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, tetrade c yl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0047] Example 13

[0048] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, tetrade c yl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0049] Example 14

[0050] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, tetrade c yl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0051] Example 15

[0052] In a reaction kettle, pyridine quaternary ammonium salt 30 parts, tetrade c yl mercaptan 11 parts, 1-hexanethiol 9 parts, OP-10 5 parts, dimethylformamide 45 parts were stirred at 45°C for 90 min, mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0053] Example 16

[0054] Pyridine quaternary ammonium salt 30 parts, tetrade-cyl mercaptan 11 parts, 1-tetradecanethiol 9 parts, OP-10 5 parts, dimethyl formamide 45 parts were stirred at 45℃ for 90 min in a reaction kettle, and mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0055] Comparative Example 1

[0056] Pyridine quaternary ammonium salt 50 parts, OP-10 5 parts, dimethyl formamide 45 parts were stirred at 45℃ for 90 min in a reaction kettle, and mixed uniformly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

[0057] Performance test:

[0058] Experimental raw material: Bohai oilfield site water.

[0059] Experimental test piece: X60 steel sheet (50mm x 30mm x 2mm).

[0060] Test method: The rotating coupon method in SY / T 5273-2000 'Performance evaluation method of corrosion inhibitor for oilfield produced water' was used to test the uniform corrosion rate and corrosion inhibition rate, the experimental temperature was 70℃, the experimental time was 72h, and the test piece linear velocity was 0.30m / s.

[0061] Experimental gas phase composition: 0.3MPa CO2+2.0MPa N2+200ppm H2S.

[0062] Medium flow rate: 1.5m / s.

[0063] Corrosion inhibitor addition amount: 30mg / L

[0064] The results are shown in Table 1.

[0065] Table 1 Corrosion rate and corrosion inhibition rate

[0066]

[0067] As can be seen from Table 1, the corrosion rate of the pyridine quaternary ammonium salt corrosion inhibitor provided by the present application is below 0.0846mm / year, the corrosion inhibition rate is above 88.90%, and the corrosion inhibitor has good corrosion inhibition effect.

[0068] Compared with Comparative Example 1, pyridine quaternary ammonium salt and mercaptan are used in Examples 1-16, and pyridine quaternary ammonium salt is used in Comparative Example 1. The corrosion rate of the pyridine quaternary ammonium salt corrosion inhibitor obtained in Examples 1-16 is lower than that of Comparative Example 1, and the corrosion inhibition rate is higher than that of Comparative Example 1, indicating that the corrosion inhibition effect of pyridine quaternary ammonium salt and mercaptan is better than that of single pyridine quaternary ammonium salt as a corrosion inhibitor.

[0069] Compared with examples 1~4, the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor obtained in examples 5~16 is better than that of examples 1~4, which indicates that the branched chain thiol and the branched chain thiol-free are compounded, and the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor can be further improved.

[0070] The corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor obtained in examples 13~15 is better than that of other examples, which indicates that when the number of carbons of the branched chain thiol is 10~14 and the number of carbons of the branched chain thiol-free is 8~12, the corrosion inhibition effect of the pyridine quaternary ammonium salt corrosion inhibitor can be further improved, and the reason may be that a more compact shielding system can be formed by adjusting the number of carbons, thereby achieving a better shielding effect.

[0071] The above only is the preferred embodiment of the present application, and does not limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A pyridine quaternary ammonium salt corrosion inhibitor for inhibiting corrosion by carbon dioxide and hydrogen sulfide, characterized in that, The product comprises the following components in parts by weight: 25-35 parts of pyridine quaternary ammonium salt, 15-25 parts of thiol, 3-8 parts of fatty alcohol polyoxyethylene ether, and 40-50 parts of solvent; the thiol includes 7-15 parts containing branched thiols and 5-13 parts without branched thiols; the mass ratio of the branched thiols to the non-branched thiols is 9:11-13:

7.

2. The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 1, characterized in that, The mass ratio of the branched thiols to the non-branched thiols is 11:

9.

3. The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 2, characterized in that, The branched thiols have 10 to 14 carbon atoms.

4. The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 3, characterized in that, The branched thiol is tert-tetradecyl thiol.

5. The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 2, characterized in that, The number of carbon atoms that do not contain branched thiols is 8 to 12.

6. The pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 5, characterized in that, The branchless thiol is 1-decylthiol.

7. A method for preparing a pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to any one of claims 1 to 6, characterized in that, The process includes the following steps: mixing the components in the specified mass fractions evenly to obtain a pyridine quaternary ammonium salt corrosion inhibitor.

8. The method for preparing a pyridine quaternary ammonium salt corrosion inhibitor for inhibiting carbon dioxide and hydrogen sulfide corrosion according to claim 7, characterized in that, The mixing temperature is 40~50℃, and the mixing time is 50~100min.

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