Composite hydrogen sulfide-resistant bactericide for oil field, and preparation method and application thereof

Abstract

The application provides a composite oilfield anti-hydrogen sulfide bactericide as well as a preparation method and application thereof. The anti-hydrogen sulfide bactericide comprises component A and component B. The component A is a bactericidal component, and the component B is an anti-hydrogen sulfide agent. The mass ratio of the component A to the component B is (1-2):(1-3). The dodecyl dimethyl benzyl ammonium chloride absorbs the cation of the ionized bacteria body, and is gathered on the cell wall to produce a room blocking effect on TGB and FB. The polyhexamethylene guanidine hydrochloride compensates for the problem that the bactericidal effect of the dodecyl dimethyl benzyl ammonium chloride on SRB is not ideal through adsorption and smothering, so that the harmful bacteria such as SRB, TGB and FB in produced water can be effectively killed. The 1,3,5-tris(hydroxyethyl)-hexahydro-sym-triazine can react with hydrogen sulfide in the produced water, and the sulfur element is bound by chemical bond to effectively reduce the hydrogen sulfide content in the produced water.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of oil field bactericides, and particularly relates to a composite oil field hydrogen sulfide-resistant bactericide and a preparation method and application thereof. BACKGROUND

[0002] In the process of oil exploitation, water injection development is generally used in oil field production to improve recovery efficiency. With the increase of produced water reinjection and various measures, the composition of the produced water in the oil field is becoming increasingly complex, containing a large amount of organic and inorganic components. Under suitable conditions, these substances can serve as nutrients for bacteria, leading to the massive reproduction of SRB, TGB, FB and other bacteria in the produced water, and intensifying the corrosion and scaling of wellbores and pipelines.

[0003] The massive reproduction of SRB will displace the sulfur in the sulfate to generate hydrogen sulfide, leading to the increasing content of hydrogen sulfide in the produced water. At the same time, due to the presence of H2S in the produced water of the sulfur-containing oil field, or due to the increase of various measures, the generation of hydrogen sulfide in the formation is intensified, leading to the increasing content of hydrogen sulfide in the produced water. Hydrogen sulfide is a toxic and harmful gas, easily soluble in water and volatile, which can cause nerve paralysis and mucosal corrosion and other hazards to the human body.

[0004] The existing bactericides are not strong in adaptability in the produced water containing hydrogen sulfide. Even if all the bacteria are killed, the hydrogen sulfide generated by the reproduction of SRB before the bactericide will cause corrosion to the subsequent pipelines and equipment, and is harmful to the human environment. SUMMARY

[0005] The present application aims to provide a composite oil field hydrogen sulfide-resistant bactericide to overcome the above technical problems in the prior art.

[0006] Another object of the present application is to provide a preparation method of the composite oil field hydrogen sulfide-resistant bactericide, which can avoid the incompatibility of component A and component B.

[0007] Another object of the present application is to provide the application of the composite oil field hydrogen sulfide-resistant bactericide in the produced water containing hydrogen sulfide in the oil field, which solves the problem of poor bactericidal effect of the existing bactericides on harmful bacteria such as SRB, TGB and FB in the produced water containing hydrogen sulfide, and can effectively reduce the hydrogen sulfide already generated in the produced water.

[0008] To this end, the technical solution provided by the present application is as follows:

[0009] A composite oil field hydrogen sulfide-resistant bactericide comprises component A and component B. The component A is a bactericidal component, and the component B is a hydrogen sulfide-resistant agent. The mass ratio of the component A to the component B is (1-2):(1-3).

[0010] The component A comprises the following mass fractions of substances: 2-5 parts of aqueous solution of polyhexamethylene guanidine hydrochloride, 1-4 parts of aqueous solution of dodecyl dimethyl benzyl ammonium chloride, and 2-3 parts of water.

[0011] The component B comprises the following mass fractions of substances: 1-3 parts of 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine, and 1-2 parts of organic solvent.

[0012] The mass concentration of polyhexamethylene guanidine hydrochloride in the aqueous solution of polyhexamethylene guanidine hydrochloride is 25%, and the mass concentration of dodecyl dimethyl benzyl ammonium chloride in the aqueous solution of dodecyl dimethyl benzyl ammonium chloride is 45%.

[0013] The organic solvent is anhydrous ethanol or methanol.

[0014] The effective mass content of the 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine is 78%.

[0015] A preparation method of a composite oilfield anti-hydrogen sulfide bactericide comprises the following steps:

[0016] Step 1) mixing polyhexamethylene guanidine hydrochloride, dodecyl dimethyl benzyl ammonium chloride and water in a certain proportion, stirring for 5-10 min, and uniformly stirring to obtain component A, wherein the aqueous solution of polyhexamethylene guanidine hydrochloride is 2-5 parts, the aqueous solution of dodecyl dimethyl benzyl ammonium chloride is 1-4 parts, and the water is 2-3 parts;

[0017] Step 2) mixing 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine and an organic solvent, stirring for 5-10 min, and uniformly stirring to obtain component B, wherein the 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazine is 1-3 parts, and the organic solvent is 1-2 parts;

[0018] Step 3) adding 1-3 parts of component B into 1-2 parts of component A, stirring for 20-30 min, and standing for 10-20 min to obtain the composite oilfield anti-hydrogen sulfide bactericide.

[0019] The application of the composite oilfield anti-hydrogen sulfide bactericide in oilfield produced water containing hydrogen sulfide.

[0020] The dosage of the composite oilfield anti-hydrogen sulfide bactericide is 50-80 mg / L.

[0021] The beneficial effects of the present application are:

[0022] The composite oil field anti-hydrogen sulfide bactericide provided by the application, the dodecyl dimethyl benzyl ammonium chloride in component A absorbs the cation ionized by the bacteria body with negative electricity, gathers on the cell wall, and has a good killing effect on TGB and FB by producing a chamber blocking effect, and the polyhexamethylene guanidine hydrochloride compensates for the problem that the dodecyl dimethyl benzyl ammonium chloride has an unsatisfactory bactericidal effect on SRB by means of adsorption and smothering, so that the harmful bacteria such as SRB, TGB and FB in produced water can be effectively killed at the same time; the 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine in component B can react with hydrogen sulfide in the produced water, and the sulfur element is bound by chemical bond, so that the content of hydrogen sulfide in the produced water is effectively reduced.

[0023] The bactericide can effectively reduce the content of hydrogen sulfide in the produced water while killing the harmful bacteria in the produced water, so that the purpose of "one dose with multiple effects" can be achieved. The bactericide has good compatibility with the oil-water system, can be mixed with the produced water at any ratio, and the ratio of component A and component B can be reasonably adjusted according to the different contents of hydrogen sulfide and bacteria in different water, so that the goal of reducing cost and increasing efficiency can be achieved.

[0024] The preparation method of the application adds component A immediately after component B is stirred uniformly, so that the components in component A and component B cannot be incompatible to form viscous flocs attached to the container wall without adding an organic solvent, which affects the effect of the prepared anti-hydrogen sulfide bactericide.

[0025] The following will be further described in detail. DETAILED DESCRIPTION

[0026] The embodiments of the application are described below by specific examples, and those skilled in the art can easily understand other advantages and effects of the application from the disclosure.

[0027] Exemplary embodiments of the application are now described in detail. The application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided by way of example so that this disclosure will convey the scope of the application to those skilled in the art. The terminology used in the detailed description of the exemplary embodiments herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0028] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0029] Example 1:

[0030] The embodiment provides a composite oilfield anti-hydrogen sulfide bactericide, which comprises component A and component B, the component A is a bactericidal component, the component B is an anti-hydrogen sulfide agent, and the mass ratio of the component A to the component B is (1-2):(1-3).

[0031] The composite oilfield anti-hydrogen sulfide bactericide provided by the embodiment can kill harmful bacteria in produced water and effectively reduce the hydrogen sulfide content in the produced water, so that the purpose of 'one agent with multiple effects' can be achieved.

[0032] The anti-hydrogen sulfide bactericide can be mixed with oilfield produced water at any ratio, and the ratio of the component A to the component B can be reasonably adjusted according to the hydrogen sulfide and bacterial content in different water quality, so that the goal of cost reduction and efficiency increase can be achieved.

[0033] Embodiment 2

[0034] On the basis of embodiment 1, the embodiment provides a composite oilfield anti-hydrogen sulfide bactericide, wherein the component A comprises the following substances in mass fraction: polyhexamethylene guanidine hydrochloride aqueous solution 2-5 parts, dodecyl dimethyl benzyl ammonium chloride aqueous solution 1-4 parts, and water 2-3 parts.

[0035] The component B comprises the following substances in mass fraction: 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine 1-3 parts and organic solvent 1-2 parts.

[0036] Principle of the application:

[0037] The dodecyl dimethyl benzyl ammonium chloride in the component A absorbs the bacteria body with negative electricity ionized by a cation and gathers on the cell wall, so that a chamber blocking effect is generated to have a good killing effect on TGB and FB, and the polyhexamethylene guanidine hydrochloride compensates for the problem that the bactericidal effect of the dodecyl dimethyl benzyl ammonium chloride on SRB is not ideal by means of adsorption and smothering, so that the harmful bacteria such as SRB, TGB and FB in the produced water can be effectively killed at the same time; the 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine in the component B can react with hydrogen sulfide in the produced water, the sulfur element is bound by chemical bond, and the hydrogen sulfide content in the produced water is effectively reduced.

[0038] The principle that the 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine absorbs H2S is as follows:

[0039]

[0040] Embodiment 3

[0041] On the basis of Embodiment 2, the present embodiment provides a composite oilfield anti-H2S bactericide, the component A comprises the following substances in mass fraction: 3 parts of aqueous solution of polyhexamethylene guanidine hydrochloride, 2 parts of aqueous solution of dodecyl dimethyl benzyl ammonium chloride, and 2 parts of water.

[0042] The component B comprises the following substances in mass fraction: 2 parts of 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine, and 2 parts of organic solvent.

[0043] In the present embodiment, the mass ratio of the component A to the component B is 1.2:1. The mass concentration of polyhexamethylene guanidine hydrochloride in the aqueous solution of polyhexamethylene guanidine hydrochloride is 25%, the mass concentration of dodecyl dimethyl benzyl ammonium chloride in the aqueous solution of dodecyl dimethyl benzyl ammonium chloride is 45%, the effective substance content of 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine is 78%, and the organic solvent is anhydrous ethanol.

[0044] Preparation process:

[0045] Step 1) preparation of component A: mix the formula amount of polyhexamethylene guanidine hydrochloride, dodecyl dimethyl benzyl ammonium chloride and water, stir for 10 minutes, and mix uniformly for standby;

[0046] Step 2) preparation of component B: add the formula amount of 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine into the formula amount of anhydrous ethanol, and stir uniformly;

[0047] Step 3) mix the uniformly stirred component A and component B according to the mass ratio of 1.2:1, stir for 30 minutes, stand for 20 minutes, and obtain.

[0048] It should be noted that the two components of component B should be added into the uniformly stirred component A immediately after being stirred uniformly, cannot be added directly without sufficient stirring, and cannot be added after standing. The reason is that the components in component A and component B will not be compatible to generate viscous floc attached to the container wall without adding organic solvent.

[0049] Embodiment 4:

[0050] On the basis of Embodiment 2, the present embodiment provides a composite oilfield anti-H2S bactericide, the component A comprises the following substances in mass fraction: 3 parts of aqueous solution of polyhexamethylene guanidine hydrochloride, 2 parts of aqueous solution of dodecyl dimethyl benzyl ammonium chloride, and 2 parts of water.

[0051] The component B comprises the following substances in mass fraction: 2 parts of 1,3,5-tris (hydroxyethyl) -hexahydro-sym-triazine, and 2 parts of organic solvent.

[0052] In the embodiment, the mass ratio of component A to component B is 1:2. The mass concentration of polyhexamethylene guanidine hydrochloride in the aqueous polyhexamethylene guanidine hydrochloride solution is 25%, the mass concentration of dodecyl dimethyl benzyl ammonium chloride in the aqueous dodecyl dimethyl benzyl ammonium chloride solution is 45%, the active substance content of 1, 3, 5-tris (hydroxyethyl) -hexahydro-sym-triazine is 78%, and the organic solvent is anhydrous ethanol.

[0053] The preparation process is the same as that in Example 3.

[0054] Example 5:

[0055] Based on Example 2, the embodiment provides a composite oilfield anti-hydrogen sulfide bactericide, the component A includes the following mass fractions of substances: 3 parts of aqueous polyhexamethylene guanidine hydrochloride solution, 4 parts of aqueous dodecyl dimethyl benzyl ammonium chloride solution, and 2 parts of water.

[0056] The component B includes the following mass fractions of substances: 1 part of 1, 3, 5-tris (hydroxyethyl) -hexahydro-sym-triazine and 1 part of an organic solvent.

[0057] In the embodiment, the mass ratio of component A to component B is 3:1. The mass concentration of polyhexamethylene guanidine hydrochloride in the aqueous polyhexamethylene guanidine hydrochloride solution is 25%, the mass concentration of dodecyl dimethyl benzyl ammonium chloride in the aqueous dodecyl dimethyl benzyl ammonium chloride solution is 45%, the active substance content of 1, 3, 5-tris (hydroxyethyl) -hexahydro-sym-triazine is 78%, and the organic solvent is anhydrous methanol.

[0058] The preparation process is the same as that in Example 4.

[0059] Example 6:

[0060] The embodiment provides application of the composite oilfield anti-hydrogen sulfide bactericide in oilfield produced water containing hydrogen sulfide.

[0061] The dosage of the composite oilfield anti-hydrogen sulfide bactericide is 50-80 mg / L.

[0062] The anti-hydrogen sulfide bactericides prepared in Example 3, Example 4 and Example 5 are subjected to application experiments, and the bactericidal and sulfur removal effects are compared with those of 1227 bactericide under the same effective concentration, and the results are shown in Table 1.

[0063] 1, the anti-hydrogen sulfide bactericide prepared in Example 3 is added into oilfield produced water containing 52 mg / L of hydrogen sulfide, 1*10 6 6 / ml of SRB, 2.5*10 3 6 / ml of TGB and 3*10 3The oil field produced water contains high oil and sundries, more than 100 mg / l, the water is light black, and pH is 6-7. 80 mg of bactericide is added to 1 L of the oil field reinjection water.

[0064] The bactericidal and sulfur removal effects of the anti-hydrogen sulfide bactericide are compared with those of 1227 bactericide (comparative example A) at the same effective concentration. The bactericidal rate is determined according to the standard requirement of SY / T 0532-93 "Oil Field Injection Water Bacterium Analysis Method Absence Dilution Method", and the sulfur removal rate is determined by using a pump suction type closed detector.

[0065] 1. The anti-hydrogen sulfide bactericide prepared in example 4 is added to oil field produced water containing 125 mg / l of hydrogen sulfide, 2.5*10 7 ml of SRB, 0.4*10 2 ml of TGB, and 0.8*10 1 ml of FB. The water quality of the on-site water sample is relatively clean, and the oil and sundries are less than about 20 mg / l, and pH is 7-8. The adding mode is that 80 mg of bactericide is added to 1 L of the oil field reinjection water.

[0066] The bactericidal and sulfur removal effects of the anti-hydrogen sulfide bactericide are compared with those of 1227 bactericide (comparative example B) at the same effective concentration. The bactericidal rate is determined according to the standard requirement of SY / T 0532-93 "Oil Field Injection Water Bacterium Analysis Method Absence Dilution Method", and the sulfur removal rate is determined by using a pump suction type closed detector.

[0067] 2. The anti-hydrogen sulfide bactericide prepared in example 4 is added to oil field produced water containing 15 mg / l of hydrogen sulfide, 1.4*10 3 ml of SRB, 4.5*10 4 ml of TGB, and 2.5*10 3 ml of FB. The water quality of the on-site water sample is relatively clean, and the oil and sundries are less than about 20 mg / l, and pH is 7-8. The adding mode is that 80 mg of bactericide is added to 1 L of the oil field reinjection water.

[0068] The bactericidal and sulfur removal effects of the anti-hydrogen sulfide bactericide are compared with those of 1227 bactericide (comparative example C) at the same effective concentration. The bactericidal rate is determined according to the standard requirement of SY / T 0532-93 "Oil Field Injection Water Bacterium Analysis Method Absence Dilution Method", and the sulfur removal rate is determined by using a pump suction type closed detector.

[0069] Table 1 Comparison of sulfur removal effects of the anti-hydrogen sulfide bactericide and 1227 bactericide

[0070]

[0071] The experimental results show that the anti-hydrogen sulfide bactericide has good bactericidal effect on SRB, TGB and FB harmful bacteria in produced water, can remove hydrogen sulfide in the produced water due to SRB breeding and formation of the stratum itself, avoids corrosion to subsequent pipeline equipment and harm to human environment.

[0072] The above examples are only illustrative of the present application and do not constitute limitation to the protection scope of the present application, and any design same as or similar to the present application belongs to the protection scope of the present application.

Claims

1. A composite oilfield hydrogen sulfide-resistant bactericide, characterized in that: It includes component A and component B, wherein component A is a bactericidal component and component B is an anti-hydrogen sulfide agent, and the mass ratio of component A to component B is (1-2):(1-3). Component A comprises the following substances in parts by mass: 2-5 parts of aqueous solution of polyhexamethylene guanidine hydrochloride, 1-4 parts of aqueous solution of dodecyl dimethyl benzyl ammonium chloride, and 2-3 parts of water; Component B comprises the following substances in parts by mass: 1,3,5-tris(hydroxyethyl)-hexahydro-triazine 1-3 parts, and an organic solvent 1-2 parts, wherein the organic solvent is anhydrous ethanol or methanol; In the preparation of this composite oilfield hydrogen sulfide-resistant bactericide, the two components of component B are immediately added to the well-stirred component A after being stirred evenly.

2. The composite oilfield hydrogen sulfide-resistant bactericide according to claim 1, characterized in that: The polyhexamethylene guanidine hydrochloride aqueous solution has a mass concentration of 25%, and the dodecyl dimethyl benzyl ammonium chloride aqueous solution has a mass concentration of 45%.

3. The composite oilfield hydrogen sulfide-resistant bactericide according to claim 1, characterized in that: The effective mass content of the 1,3,5-tris(hydroxyethyl)-hexahydro-triazine is 78%.

4. A method for preparing a composite oilfield hydrogen sulfide-resistant bactericide according to any one of claims 1-3, characterized in that, Includes the following steps: Step 1) Mix polyhexamethylene guanidine hydrochloride, dodecyl dimethyl benzyl ammonium chloride and water in a certain proportion, stir for 5-10 minutes, and set aside after stirring evenly to obtain component A, wherein the aqueous solution of polyhexamethylene guanidine hydrochloride is 2-5 parts, the aqueous solution of dodecyl dimethyl benzyl ammonium chloride is 1-4 parts, and the water is 2-3 parts. Step 2) Mix 1,3,5-tris(hydroxyethyl)-hexahydro-triazine and organic solvent and stir for 5-10 minutes until homogeneous to obtain component B, wherein 1-3 parts of 1,3,5-tris(hydroxyethyl)-hexahydro-triazine and 1-2 parts of organic solvent are used. Step 3) Add 1-3 parts of component B to 1-2 parts of component A, stir for 20-30 minutes, and let stand for 10-20 minutes to obtain the final product.

5. The application of a composite oilfield hydrogen sulfide-resistant bactericide according to any one of claims 1-3 in produced water from oilfields containing hydrogen sulfide.

6. The application of the composite oilfield hydrogen sulfide-resistant bactericide according to claim 5 in produced water from oilfields containing hydrogen sulfide, characterized in that: The dosage of compound oilfield hydrogen sulfide resistant bactericide is 50-80 mg / L.

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