Oil and gas field sterilization desulfurizer and preparation method thereof

Abstract

The invention discloses an oil and gas field sterilization desulfurizer and a preparation method thereof, and relates to the technical field of oil and gas field chemicals, and the oil and gas field sterilization desulfurizer is prepared from the following components: hexahydrotriazine, amphoteric organic ionic salt, hydroxypropyl beta-cyclodextrin, hexamethylenetetramine, adenosine, 2-hydrazinoethanol, N, N '-bis (2-ethoxyl) piperazine, 1, 3, 5, 6-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5 The scale inhibitor is prepared from 1, 3, 5-tris (2-hydroxyethyl) cyanuric acid, diazoalkyl urea, soluble ferric salt, a scale inhibitor, a triazine degradation inhibitor, hydroxypropyl trimethyl ammonium chloride chitosan and water. The oil and gas field sterilizing and desulfurizing agent is high in desulfurizing efficiency, good in sterilizing effect, low in dosage, good in scale and corrosion inhibition performance and safe and environment-friendly to use.

Description

Technical Field

[0001] The invention relates to the technical field of oil and gas field chemicals, and in particular to an oil and gas field sterilization and desulfurization agent and a preparation method thereof. Background Art

[0002] During the exploitation of oil and gas fields, crude oil contains a certain amount of hydrogen sulfide and organic sulfides such as methyl mercaptan, ethyl mercaptan, and carbonyl sulfide. These sulfides in crude oil decompose to produce low-grade sulfides such as hydrogen sulfide during the collection, transportation, and processing of crude oil, and bacteria continue to grow. Hydrogen sulfide and bacteria not only have adverse effects on the properties of crude oil, but also cause chemical corrosion and stress corrosion of equipment and pipelines, causing leakage of equipment and pipelines, seriously affecting production safety and threatening the lives and health of personnel, causing huge economic losses every year.

[0003] In order to solve the above problems, the most effective and convenient way is to add a bactericidal desulfurizer to the oil and gas field. However, the existing bactericidal desulfurizers for oil and gas fields have more or less low desulfurization efficiency, large dosage and drug resistance, the bactericidal effect needs to be further improved, poor compatibility, and precipitation when the local H2S concentration is high, causing pipeline blockage and other technical defects. For example, the Chinese invention patent with the authorization announcement number CN107418641B discloses a high-temperature resistant desulfurizer for oil and gas fields and a preparation method thereof, first weighing 30-60% of a triazine compound, 5-20% of an organic phosphonic acid, 5-20% of a heterocyclic organic amine, 5-20% of a water-soluble imidazoline, and the rest is water, and the total mass percentage of the above components is 100%; then the triazine compound is added to the water and stirred evenly to obtain a mixture B; then the heterocyclic organic amine, the water-soluble imidazoline and the organic phosphonic acid are added to the mixture B in sequence, and stirred evenly to obtain a high-temperature resistant desulfurizer for oil and gas fields. The desulfurizer prepared by the invention has high desulfurization efficiency under high temperature conditions of 90°C; and the product also has certain anti-scaling, corrosion-inhibiting and bactericidal properties; the pH value of the prepared desulfurizer is 7-8, which can delay the scaling trend of carbonates and sulfates in high-mineralization water environments; the entire synthesis process is simple, easy to operate, low in cost, non-toxic and environmentally friendly, and suitable for industrial production. However, its bactericidal effect still needs to be further improved.

[0004] It can be seen that the development of an oil and gas field sterilization and desulfurization agent with high desulfurization efficiency, good sterilization effect, low dosage, good scale and corrosion inhibition performance, safe and environmentally friendly use and its preparation method meets market demand, has broad market value and application prospects, and is of great significance to promoting the development of oil and gas field exploitation and gathering and transportation. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and to provide an oil and gas field sterilization and desulfurization agent with high desulfurization efficiency, good sterilization effect, low dosage, good scale and corrosion inhibition performance, safe use and environmental protection, and a preparation method thereof.

[0006] To achieve the above object, the technical scheme adopted by the present invention is: an oil and gas field sterilization and desulfurization agent, comprising the following components in weight percentage: 20wt%-30wt% of hydroxyethyl hexahydro-s-triazine, 3wt%-5wt% of amphoteric organic ion salt, 0.3wt%-1.2wt% of hydroxypropyl β-cyclodextrin, 1wt%-3wt% of hexamethylenetetramine, 0.1wt%-0.3wt% of adenosine, 3wt%-5wt% of 2-hydrazinoethanol t%, N,N'-bis(2-hydroxyethyl)piperazine 5wt%-8wt%, 1,3,5-tris(2-hydroxyethyl)cyanuric acid 0.1wt%-0.3wt%, diazolidinyl urea 0.1wt%-0.3wt%, soluble iron salt 2wt%-4wt%, scale inhibitor 1wt%-3wt%, triazine degradation inhibitor 0.2wt%-0.5wt%, hydroxypropyltrimethylammonium chloride chitosan 1wt%-3wt%, and the balance is water.

[0007] Preferably, the amphoteric organic ion salt is at least one of glycerolphosphorylcholine and hydroxypropane sulfonate pyridinium salt.

[0008] Preferably, the soluble iron salt is one or more combinations of ferric nitrate, ferric chloride and ferric sulfate.

[0009] Preferably, the scale inhibitor is hydroxyethylidene diphosphonic acid.

[0010] Preferably, the triazine degradation inhibitor is ethoxylated isomeric tridecanol.

[0011] Preferably, the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0012] Another object of the present invention is to provide a method for preparing the oil and gas field sterilization and desulfurization agent, comprising the following steps: uniformly mixing the components according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0013] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0014] (1) The preparation method of the oil and gas field bactericidal desulfurizer disclosed in the present invention only requires mixing the components uniformly according to weight percentage, does not require special equipment, consumes less energy and capital investment, has high preparation efficiency and finished product qualification rate, has low labor intensity, has little impact on the environment, and is suitable for continuous large-scale production.

[0015] (2) The oil and gas field sterilization and desulfurization agent disclosed in the present invention comprises the following components in percentage by weight: 20wt%-30wt% of hydroxyethyl hexahydro-s-triazine, 3wt%-5wt% of amphoteric organic ion salt, 0.3wt%-1.2wt% of hydroxypropyl β-cyclodextrin, 1wt%-3wt% of hexamethylenetetramine, 0.1wt%-0.3wt% of adenosine, 3wt%-5wt% of 2-hydrazinoethanol, 5wt%-8wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.1wt%-0.3wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.1wt%-0.3wt% of diazolidinyl urea, 2wt%-4wt% of soluble iron salt, 1wt%-3wt% of scale inhibitor, 0.2wt%-0.5wt% of triazine degradation inhibitor, 1wt%-3wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water. Through the mutual coordination and joint action of various components, the produced oil and gas field sterilization and desulfurization agent has high desulfurization efficiency, good sterilization effect, low dosage, good scale and corrosion inhibition performance, and is safe and environmentally friendly to use.

[0016] (3) The oil and gas field sterilization and desulfurization agent disclosed in the present invention can improve stability by selecting appropriate components and rationally matching with triazine compounds, so that the product has a long shelf life and is not easily degraded during long-term storage, and will not cause scaling problems in oil pipes, casings, and wellbores, so that the product has a good sterilization and desulfurization effect even at higher temperatures. DETAILED DESCRIPTION

[0017] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0018] Example 1

[0019] The invention discloses an oil and gas field sterilization and desulfurization agent, which comprises the following components in percentage by weight: 20 wt% of hydroxyethyl hexahydro-s-triazine, 3 wt% of amphoteric organic ion salt, 0.3 wt% of hydroxypropyl beta-cyclodextrin, 1 wt% of hexamethylenetetramine, 0.1 wt% of adenosine, 3 wt% of 2-hydrazinoethanol, 5 wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.1 wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.1 wt% of diazolidinyl urea, 2 wt% of soluble iron salt, 1 wt% of scale inhibitor, 0.2 wt% of triazine degradation inhibitor, 1 wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

[0020] The amphoteric organic ion salt is glycerolphosphorylcholine; the soluble iron salt is ferric nitrate; the scale inhibitor is hydroxyethylidene diphosphonic acid; the triazine degradation inhibitor is ethoxylated isomeric tridecanol; the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0021] A method for preparing the oil and gas field sterilization and desulfurization agent comprises the following steps: mixing the components uniformly according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0022] Example 2

[0023] An oil and gas field sterilization and desulfurization agent comprises the following components in percentage by weight: 23 wt% of hydroxyethyl hexahydro-s-triazine, 3.5 wt% of amphoteric organic ion salt, 0.5 wt% of hydroxypropyl beta-cyclodextrin, 1.5 wt% of hexamethylenetetramine, 0.15 wt% of adenosine, 3.5 wt% of 2-hydrazinoethanol, 6 wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.15 wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.15 wt% of diazolidinyl urea, 2.5 wt% of soluble iron salt, 1.5 wt% of scale inhibitor, 0.3 wt% of triazine degradation inhibitor, 1.5 wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

[0024] The amphoteric organic ion salt is hydroxypropane sulfonic acid pyridinium salt; the soluble iron salt is ferric chloride; the scale inhibitor is hydroxyethylidene diphosphonic acid; the triazine degradation inhibitor is ethoxylated isomeric tridecanol; the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0025] A method for preparing the oil and gas field sterilization and desulfurization agent comprises the following steps: mixing the components uniformly according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0026] Example 3

[0027] The invention discloses an oil and gas field sterilization and desulfurization agent, which comprises the following components in percentage by weight: 25 wt% of hydroxyethyl hexahydro-s-triazine, 4 wt% of amphoteric organic ion salt, 0.8 wt% of hydroxypropyl beta-cyclodextrin, 2 wt% of hexamethylenetetramine, 0.2 wt% of adenosine, 4 wt% of 2-hydrazineethanol, 6.5 wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.2 wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.2 wt% of diazolidinyl urea, 3 wt% of soluble iron salt, 2 wt% of scale inhibitor, 0.35 wt% of triazine degradation inhibitor, 2 wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

[0028] The amphoteric organic ion salt is glycerolphosphorylcholine; the soluble iron salt is ferric sulfate; the scale inhibitor is hydroxyethylidene diphosphonic acid; the triazine degradation inhibitor is ethoxylated isomeric tridecanol; the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0029] A method for preparing the oil and gas field sterilization and desulfurization agent comprises the following steps: mixing the components uniformly according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0030] Example 4

[0031] An oil and gas field sterilization and desulfurization agent comprises the following components in percentage by weight: 28 wt% of hydroxyethyl hexahydro-s-triazine, 4.5 wt% of amphoteric organic ion salt, 1 wt% of hydroxypropyl beta-cyclodextrin, 2.5 wt% of hexamethylenetetramine, 0.25 wt% of adenosine, 4.5 wt% of 2-hydrazinoethanol, 7.5 wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.25 wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.25 wt% of diazolidinyl urea, 3.5 wt% of soluble iron salt, 2.5 wt% of scale inhibitor, 0.45 wt% of triazine degradation inhibitor, 2.5 wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

[0032] The amphoteric organic ion salt is a mixture of glycerolphosphorylcholine and hydroxypropane sulfonate pyridinium salt in a mass ratio of 3:5; the soluble iron salt is a mixture of ferric nitrate, ferric chloride and ferric sulfate in a mass ratio of 1:2:3; the scale inhibitor is hydroxyethylidene diphosphonic acid; the triazine degradation inhibitor is ethoxylated isomeric tridecanol; the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0033] A method for preparing the oil and gas field sterilization and desulfurization agent comprises the following steps: mixing the components uniformly according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0034] Example 5

[0035] The invention discloses an oil and gas field sterilization and desulfurization agent, which comprises the following components in percentage by weight: 30 wt% of hydroxyethyl hexahydro-s-triazine, 5 wt% of amphoteric organic ion salt, 1.2 wt% of hydroxypropyl beta-cyclodextrin, 3 wt% of hexamethylenetetramine, 0.3 wt% of adenosine, 5 wt% of 2-hydrazinoethanol, 8 wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.3 wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.3 wt% of diazolidinyl urea, 4 wt% of soluble iron salt, 3 wt% of scale inhibitor, 0.5 wt% of triazine degradation inhibitor, 3 wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

[0036] The amphoteric organic ion salt is glycerolphosphorylcholine; the soluble iron salt is ferric nitrate; the scale inhibitor is hydroxyethylidene diphosphonic acid; the triazine degradation inhibitor is ethoxylated isomeric tridecanol; the number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

[0037] A method for preparing the oil and gas field sterilization and desulfurization agent comprises the following steps: mixing the components uniformly according to weight percentage to obtain the oil and gas field sterilization and desulfurization agent.

[0038] Comparative Example 1

[0039] An oil and gas field sterilization and desulfurization agent and a preparation method thereof are basically the same as those in Example 1, except that no amphoteric organic ion salt and diazolidinyl urea are added.

[0040] Comparative Example 2

[0041] An oil and gas field sterilization and desulfurization agent and a preparation method thereof are substantially the same as those in Example 1, except that hydroxypropyl beta-cyclodextrin and hydroxypropyl trimethylammonium chloride chitosan are not added.

[0042] In order to further illustrate the beneficial technical effects of the oil and gas field sterilization and desulfurization agent involved in each embodiment of the present invention, the relevant performance tests were carried out on the oil and gas field sterilization and desulfurization agents involved in Examples 1-5 and Comparative Examples 1-2; the evaluation of the desulfurization effect was based on GB / T11060.11-2014 "Determination of sulfur compounds in natural gas Part 11: Determination of hydrogen sulfide content by coloring length detection tube method", and the desulfurization ability of the oil and gas field sterilization and desulfurization agent prepared by the present invention in the produced fluid of high-sulfur oil wells was tested at 90°C using a hydrogen sulfide test tube. The agent concentration was 500 mg / L, the initial hydrogen sulfide concentration was 7000 ppm, the residual hydrogen sulfide concentration after 10 minutes was calculated, and the desulfurization rate was calculated. The sterilization performance test was based on SY / T 49-2010 "Technical Requirements for Bactericides for Oil Fields", and the experimental raw materials used were bacterial water samples from a certain oil and gas field site, and the blank SRB bacterial content was 0.5×10 5 / mL, the evaluation method is the extinction dilution method, the experimental temperature is 45℃, the test time is 168 hours, the agent concentration is 50mg / L, and the sterilization rate is counted and calculated. Refer to SY / T5673-1993 Performance Evaluation Method of Antiscalant for Oil and Gas Fields. According to the experimental conditions, take the corresponding 100ml test medium and add it to the stoppered colorimetric tube, the desulfurizer filling concentration is 200mg / L, heat it to the test temperature of 55℃, and keep the temperature constant for 48 hours. After the temperature cools down, observe the scaling of the medium in the colorimetric tube.

[0043] As can be seen from Table 1, the oil and gas field sterilization and desulfurization agents involved in the embodiments of the present invention have better sterilization and desulfurization effects than the comparative products, and do not scale. The combined use of amphoteric organic ion salts, diazolidinyl urea, hydroxypropyl β-cyclodextrin and hydroxypropyl trimethyl ammonium chloride chitosan is beneficial to improving the above performance.

[0044] Table 1

[0045] project Desulfurization rate Sterilization rate Scaling unit ％ ％ — Example 1 99.90 99.93 No scaling Example 2 99.94 99.96 No scaling Example 3 99.96 99.97 No scaling Example 4 99.97 99.99 No scaling Example 5 99.99 99.99 No scaling Comparative Example 1 99.43 98.87 Micro-scaling Comparative Example 2 99.11 97.14 Micro-scaling

[0046] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A bactericidal desulfurizer for oil and gas fields, It is characterized in that The invention comprises the following components in percentage by weight: 20wt%-30wt% of hydroxyethyl hexahydro-s-triazine, 3wt%-5wt% of amphoteric organic ion salt, 0.3wt%-1.2wt% of hydroxypropyl beta-cyclodextrin, 1wt%-3wt% of hexamethylenetetramine, 0.1wt%-0.3wt% of adenosine, 3wt%-5wt% of 2-hydrazinoethanol, 5wt%-8wt% of N,N'-bis(2-hydroxyethyl)piperazine, 0.1wt%-0.3wt% of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 0.1wt%-0.3wt% of diazolidinyl urea, 2wt%-4wt% of soluble iron salt, 1wt%-3wt% of scale inhibitor, 0.2wt%-0.5wt% of triazine degradation inhibitor, 1wt%-3wt% of hydroxypropyltrimethylammonium chloride chitosan, and the balance is water.

2. The oil and gas field sterilization and desulfurization agent according to claim 1, It is characterized in that The amphoteric organic ion salt is at least one of glycerol phosphorylcholine and hydroxypropane sulfonate pyridinium salt.

3. The oil and gas field sterilization and desulfurization agent according to claim 1, It is characterized in that The soluble iron salt is one or more combinations of ferric nitrate, ferric chloride and ferric sulfate.

4. The oil and gas field sterilization and desulfurization agent according to claim 1, It is characterized in that The scale inhibitor is hydroxyethylidene diphosphonic acid.

5. The oil and gas field sterilization and desulfurization agent according to claim 1, It is characterized in that The triazine degradation inhibitor is ethoxylated isomeric tridecanol.

6. The oil and gas field sterilization and desulfurization agent according to claim 1, It is characterized in that The number average molecular weight of the hydroxypropyltrimethylammonium chloride chitosan is 100,000, and the degree of substitution is 90%.

7. A method for preparing the oil and gas field sterilization and desulfurization agent according to any one of claims 1 to 6, It is characterized in that The method comprises the following steps: mixing the components uniformly according to weight percentage to obtain an oil and gas field sterilization and desulfurization agent.