Hydrogen sulfide corrosion inhibitor and preparation method thereof

Abstract

The invention discloses a hydrogen sulfide corrosion inhibitor and a preparation method thereof, and belongs to the technical field of oilfield chemistry. The hydrogen sulfide corrosion inhibitor is prepared from the following components in parts by weight: 35 to 50 parts of alkyne oxygen thiol compound, 25 to 40 parts of chlorinated benzyl quinoline quaternary ammonium salt and 20 to 30 parts of surfactant, and the surfactant is at least one of OP-10, AEO-10, NP-10 and TX-10. The preparation method of the hydrogen sulfide corrosion inhibitor comprises the following steps: slowly adding the metal sodium wire into the propargyl alcohol, controlling the temperature to be a first set temperature in the adding process, controlling the temperature to be a second set temperature after the metal sodium wire is added, and continuously reacting for a set time to obtain a sodium propargyl alcohol product; taking the sodium propargyl alcohol product and 3-chloro-1-propanethiol as reactants, and carrying out chlorination reaction to obtain an alkyne oxygen thiol compound; the preparation method comprises the following steps: stirring and mixing the alkyne oxythiol compound, the chlorinated benzyl quinoline quaternary ammonium salt and the surfactant to obtain the hydrogen sulfide corrosion inhibitor.

Description

Technical Field

[0001] The invention belongs to the technical field of oilfield chemistry, and in particular relates to a hydrogen sulfide corrosion inhibitor and a preparation method thereof. Background Art

[0002] With the deepening of oil and gas field exploitation, more and more oil and gas fields with high hydrogen sulfide content have emerged. Hydrogen sulfide is highly corrosive to metals. Hydrogen sulfide corrosion can cause damage to pipelines and equipment, resulting in economic losses. After hydrogen sulfide leaks, due to its flammable, explosive and highly toxic properties, it can cause serious safety accidents and environmental damage. At present, hydrogen sulfide corrosion has become one of the biggest problems faced in the exploitation of high-sulfur oil and gas fields. Adding corrosion inhibitors to inhibit corrosion is a very common method in oil and gas fields, but the most widely used imidazoline corrosion inhibitor in oil fields is not ideal for inhibiting hydrogen sulfide corrosion. Therefore, an efficient hydrogen sulfide corrosion inhibitor is prepared, which will ensure the smooth and safe exploitation of high-sulfur oil and gas fields. Summary of the invention

[0003] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a hydrogen sulfide corrosion inhibitor and a preparation method thereof, wherein the corrosion inhibitor prepared by using acetylene oxide mercaptan compounds can effectively inhibit the corrosion of hydrogen sulfide, and the corrosion inhibitor has a small dosage, a significant corrosion inhibition effect, and good resistance to high-temperature hydrogen sulfide corrosion, so as to solve the technical problem that the inhibitory effect of the existing commonly used imidazoline corrosion inhibitor on hydrogen sulfide corrosion is not ideal.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] The present invention provides a hydrogen sulfide corrosion inhibitor, which comprises, by weight, 35 to 50 parts of an acetylene oxide mercaptan compound, 25 to 40 parts of a benzylquinoline quaternary ammonium chloride salt, and 20 to 30 parts of a surfactant;

[0006] The alkynyloxythiol compound has the structural formula (I):

[0007]

[0008] In a specific implementation process, the surfactant is at least one of OP-10, AEO-10, NP-10 and TX-10.

[0009] The present invention also provides a method for preparing the hydrogen sulfide corrosion inhibitor according to any one of the above, comprising the following steps:

[0010] S1: slowly adding the metal sodium wire to the propargyl alcohol, controlling the temperature to a first set temperature during the adding process, and controlling the temperature to a second set temperature after the addition of the metal sodium wire is completed and continuing the reaction for a set time to obtain a sodium propargyl alcohol product;

[0011] S2: using the sodium propargyl alcohol product and 3-chloro-1-propanethiol as reactants to carry out a chlorination reaction to obtain an alkynyloxythiol compound;

[0012] S3: stirring and mixing the alkynyloxythiol compound, benzylquinoline quaternary ammonium chloride and a surfactant according to weight proportions to obtain a hydrogen sulfide corrosion inhibitor.

[0013] In a specific implementation process, the mass ratio of the propargyl alcohol to the metallic sodium wire is (2-4):1.

[0014] In the specific implementation process, the first set temperature is 30-60°C; the second set temperature is 50-70°C; and the set time is 3-5h.

[0015] In the specific implementation process, the mass ratio of the sodium propargyl alcohol product to 3-chloro-1-propanethiol is (1-1.2):1.

[0016] In the specific implementation process, the reaction temperature of the chlorination reaction is 80-100° C.; the reaction time of the chlorination reaction is 8-12 hours.

[0017] In the specific implementation process, the sodium propargyl alcohol product has the structural formula of the following formula (II):

[0018] HC≡CO-Na(II).

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention provides a hydrogen sulfide corrosion inhibitor and a preparation method thereof, which is obtained by reprocessing an acetylene oxide mercaptan compound as a raw material, wherein the acetylene oxide mercaptan compound is an important component of the corrosion inhibitor for exerting a corrosion inhibition effect; the corrosion inhibitor can effectively inhibit the corrosion of hydrogen sulfide to metals, and the hydrogen sulfide corrosion inhibitor has a small dosage, a significant corrosion inhibition effect, and good resistance to high temperature and high pressure hydrogen sulfide corrosion. The above hydrogen sulfide corrosion inhibitor can be used in a process environment containing a hydrogen sulfide partial pressure of 0.1 MPa to 1 MPa at room temperature (such as 20°C) to 80°C, and the hydrogen sulfide corrosion inhibitor of the present invention can be directly added to the corrosive medium. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0023] Herein, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0024] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0025] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0026] The invention provides a hydrogen sulfide corrosion inhibitor and a preparation method thereof.

[0027] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0028] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0029] The first aspect of the present invention provides a hydrogen sulfide corrosion inhibitor, comprising 35 to 50 parts of an acetylene oxide mercaptan compound, 25 to 40 parts of a benzylquinoline quaternary ammonium chloride salt and 20 to 30 parts of a surfactant; in a specific implementation process, the surfactant is at least one of OP-10, AEO-10, NP-10 and TX-10.

[0030] The alkynyloxythiol compound has the structural formula (I):

[0031]

[0032] The preparation method of the above-mentioned alkynyloxythiol compound is as follows:

[0033] S1: using propargyl alcohol and metallic sodium wire in a mass ratio of (2-4):1 as raw materials, slowly adding the metallic sodium wire into the propargyl alcohol, controlling the temperature at 30-60°C during the adding process, and controlling the temperature at 50-70°C after the addition of the metallic sodium wire, and continuing the reaction for 3-5h to obtain a sodium propargyl alcohol product;

[0034] The above-mentioned sodium propargyl alcohol product has the structural formula of the following formula (II):

[0035] HC≡CO-Na(II).

[0036] S2: Using sodium propargyl alcohol product and 3-chloro-1-propanethiol in a mass ratio of (1-1.2):1 as reactants, the reactants are subjected to chlorination reaction at 80-100° C. for 8-12 hours to obtain an alkynyloxythiol compound.

[0037] A second aspect of the present invention provides a method for preparing a hydrogen sulfide corrosion inhibitor, comprising the following steps:

[0038] According to the above preparation method, an alkynyloxythiol compound is prepared, and 35 to 50 parts of the alkynyloxythiol compound, 25 to 40 parts of benzylquinoline quaternary ammonium chloride and 20 to 30 parts of a surfactant are stirred and mixed according to weight parts to obtain a hydrogen sulfide corrosion inhibitor.

[0039] The invention obtains a highly efficient hydrogen sulfide corrosion inhibitor by improving the preparation of a key acetylene oxide thiol compound, the application of the acetylene oxide thiol compound and its application mode (such as the proportion of the acetylene oxide thiol compound in the corrosion inhibitor and the proportion of other constituent raw materials).

[0040] The present invention uses an acetylene oxide mercaptan compound as an important component of a hydrogen sulfide corrosion inhibitor. The corrosion inhibitor prepared by using the acetylene oxide mercaptan compound can effectively inhibit hydrogen sulfide corrosion, and the corrosion inhibitor has a small dosage, a significant corrosion inhibition effect, and good resistance to high-temperature hydrogen sulfide corrosion.

[0041] Example 1

[0042] Put 75g of propargyl alcohol into a three-necked flask, start stirring, and slowly add 25g of sodium wire. During the addition process, control the reaction temperature to 45±2℃. After the addition is completed, raise the temperature to 55℃ and continue the reaction for 3 hours to obtain sodium propargyl alcohol product.

[0043] 50 g of the sodium propargyl alcohol product prepared above and 50 g of 3-chloro-1-propanethiol were put into a three-necked flask, the temperature was raised to 90° C., and the temperature was maintained for 10 hours to obtain an alkynyloxythiol compound.

[0044] 40 g of the acetylene oxide mercaptan compound prepared above, 30 g of benzylquinoline quaternary ammonium chloride, and 30 g of OP-10 were added to a three-necked flask and stirred to obtain 100 g of hydrogen sulfide corrosion inhibitor.

[0045] Corrosion inhibition performance evaluation:

[0046] The corrosion inhibition performance was evaluated according to the industry standard SY / T 5273-2000.

[0047] Table 1 shows the comparative evaluation results of the corrosion inhibitor prepared in Example 1 and commercially available oleic acid-based imidazoline.

[0048] Table 1

[0049]

[0050] It can be seen from the test data in Table 1 that, under the same conditions, the corrosion inhibition performance of the corrosion inhibitor of the present invention in corrosive media is far superior to that of commercially available oleic acid imidazoline, and the corrosion inhibitor of the present invention can meet the industry requirement that the corrosion rate is not greater than 0.076 mm / a.

[0051] Example 2

[0052] Put 40 grams of propargyl alcohol into a three-necked flask, start stirring, and slowly add 10 grams of sodium wire. During the addition process, control the reaction temperature to 30±2°C. After the addition is completed, raise the temperature to 50°C and continue the reaction for 3 hours to obtain sodium propargyl alcohol product.

[0053] 55 g of the sodium propargyl alcohol product prepared above and 45 g of 3-chloro-1-propanethiol were put into a three-necked flask, the temperature was raised to 80° C., and the temperature was maintained for 8 hours to obtain an alkynyloxythiol compound.

[0054] 35 g of the acetylene oxide mercaptan compound prepared above, 40 g of benzylquinoline quaternary ammonium chloride, and 25 g of OP-10 were added to a three-necked flask and stirred to obtain 100 g of hydrogen sulfide corrosion inhibitor.

[0055] Corrosion inhibition performance evaluation:

[0056] The corrosion inhibition performance was evaluated according to the industry standard SY / T 5273-2000.

[0057] Table 2 shows the comparative evaluation results of the corrosion inhibitor prepared in Example 2 and commercially available imidazoline phosphate.

[0058] Table 2

[0059]

[0060] It can be seen from the test data in Table 2 that, under the same conditions, the corrosion inhibition performance of the corrosion inhibitor of the present invention in hydrogen sulfide corrosive media is much better than that of commercially available imidazoline phosphate products, and the corrosion inhibitor of the present invention can meet the industry requirement of a corrosion rate of no more than 0.076 mm / a.

[0061] Example 3

[0062] Put 67 grams of propargyl alcohol into a three-necked flask, start stirring, and slowly add 23 grams of sodium wire. During the addition process, control the reaction temperature to 60±2°C. After the addition is completed, raise the temperature to 70°C and continue the reaction for 5 hours to obtain sodium propargyl alcohol product.

[0063] 52 g of the sodium propargyl alcohol product prepared above and 48 g of 3-chloro-1-propanethiol were put into a three-necked flask, the temperature was raised to 100° C., and the temperature was maintained for 12 hours to obtain an alkynyloxythiol compound.

[0064] 50 g of the acetylene oxide mercaptan compound prepared above, 25 g of benzylquinoline quaternary ammonium chloride, and 25 g of OP-10 were added to a three-necked flask and stirred to obtain 100 g of hydrogen sulfide corrosion inhibitor.

[0065] Corrosion inhibition performance evaluation:

[0066] The corrosion inhibition performance was evaluated according to the industry standard SY / T 5273-2000.

[0067] Table 3 shows the comparative evaluation results of the corrosion inhibitor prepared in Example 3 and commercially available thiourea-based imidazoline.

[0068] Table 3

[0069]

[0070]

[0071] It can be seen from the test data in Table 3 that under the same conditions, the corrosion inhibition performance of the corrosion inhibitor of the present invention in a hydrogen sulfide-containing medium environment is far superior to that of the commercially available thiourea-based imidazoline product. At the same time, the corrosion inhibitor of the present invention can meet the industry requirement that the corrosion rate is not greater than 0.076 mm / a.

[0072] Example 4

[0073] Put 50 grams of propargyl alcohol into a three-necked flask, start stirring, and slowly add 25 grams of sodium wire. During the addition process, control the reaction temperature to 45±2°C. After the addition is completed, raise the temperature to 55°C and continue the reaction for 3 hours to obtain sodium propargyl alcohol product.

[0074] 50 g of the sodium propargyl alcohol product prepared above and 50 g of 3-chloro-1-propanethiol were put into a three-necked flask, the temperature was raised to 90° C., and the temperature was maintained for 10 hours to obtain an alkynyloxythiol compound.

[0075] 40 g of the acetylene oxide mercaptan compound prepared above, 30 g of benzylquinoline quaternary ammonium chloride, and 30 g of OP-10 were added to a three-necked flask and stirred to obtain 100 g of hydrogen sulfide corrosion inhibitor.

[0076] The surfactant may be at least one of OP-10, AEO-10, NP-10 and TX-10.

[0077] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A hydrogen sulfide corrosion inhibitor, It is characterized in that In parts by weight, the hydrogen sulfide corrosion inhibitor comprises 35 to 50 parts of an alkynyloxythiol compound, 25 to 40 parts of a benzylquinoline quaternary ammonium chloride salt, and 20 to 30 parts of a surfactant; The alkynyloxythiol compound has the structural formula (I):

2. The hydrogen sulfide corrosion inhibitor according to claim 1, It is characterized in that The surfactant is at least one of OP-10, AEO-10, NP-10 and TX-10.

3. The method for preparing the hydrogen sulfide corrosion inhibitor according to any one of claims 1 to 2, It is characterized in that The following steps are involved: S1: slowly adding the metal sodium wire to the propargyl alcohol, controlling the temperature to a first set temperature during the adding process, and controlling the temperature to a second set temperature after the addition of the metal sodium wire is completed and continuing the reaction for a set time to obtain a sodium propargyl alcohol product; S2: using the sodium propargyl alcohol product and 3-chloro-1-propanethiol as reactants to carry out a chlorination reaction to obtain an alkynyloxythiol compound; S3: stirring and mixing the alkynyloxythiol compound, benzylquinoline quaternary ammonium chloride and a surfactant according to weight proportions to obtain a hydrogen sulfide corrosion inhibitor.

4. The method for preparing the hydrogen sulfide corrosion inhibitor according to claim 3, It is characterized in that The mass ratio of the propargyl alcohol to the metallic sodium wire is (2-4):

1.

5. The method for preparing the hydrogen sulfide corrosion inhibitor according to claim 3, It is characterized in that The first set temperature is 30-60° C.; the second set temperature is 50-70° C.; and the set time is 3-5 hours.

6. The method for preparing the hydrogen sulfide corrosion inhibitor according to claim 3, It is characterized in that The mass ratio of the sodium propargyl alcohol product to 3-chloro-1-propanethiol is (1-1.2):

1.

7. The method for preparing the hydrogen sulfide corrosion inhibitor according to claim 3, It is characterized in that The reaction temperature of the chlorination reaction is 80-100° C.; the reaction time of the chlorination reaction is 8-12 hours.

8. The method for preparing the hydrogen sulfide corrosion inhibitor according to claim 3, It is characterized in that The sodium propargyl alcohol product has the structural formula (II):

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