CN114456522A - Rubber composition for resisting hydrogen sulfide corrosion of oil and gas fields - Google Patents
Rubber composition for resisting hydrogen sulfide corrosion of oil and gas fields Download PDFInfo
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Abstract
The invention relates to the field of rubber products for hydrogen sulfide-containing oil and gas fields, and discloses a hydrogen sulfide corrosion-resistant rubber composition for oil and gas fields, which comprises the following components in parts by mass: 100 parts of main material, 1-2 parts of processing aid, 2-6 parts of cross-linking agent, 1.5-4 parts of anti-aging agent, 20-80 parts of reinforcing filler, 2-20 parts of sulfur-resistant agent, 2-8 parts of auxiliary cross-linking agent and 2-5 parts of flow modifier; the main material is tetrafluoroethylene-propylene rubber; the cross-linking agent is organic peroxide; the reinforcing filler is carbon black; the sulfur-resistant agent is a carbon nano tube. The rubber composition obtained by reasonably composing the tetrapropylene fluoride rubber serving as the main material has excellent comprehensive performance, particularly the carbon nano tube is used as the sulfur-resistant agent, so that the rubber composition has excellent hydrogen sulfide corrosion resistance, and can be successfully used in the oil-gas well environment with the temperature of 150 ℃, the pressure of 70MPa and the partial pressure of hydrogen sulfide of 15 MPa.
Description
Technical Field
The invention relates to the field of rubber products for hydrogen sulfide-containing oil and gas fields, in particular to a rubber composition for resisting hydrogen sulfide corrosion in the oil and gas fields.
Background
In recent decades, oil and gas fields containing hydrogen sulfide corrosion medium have been in succession, and the corrosion problem has attracted more and more attention. The corrosion not only causes great economic loss for the development and production of oil and gas fields, but also causes environmental pollution and threatens the personal safety. In the early stage of the 80's of the 20 th century, natural gas containing hydrogen sulfide, which was ascertained in China, accounts for 1/4 of the reserves of the gas layer in China. In recent years, high-sulfur-content oil and gas fields are continuously discovered in the exploration work of China. The appearance of high-sulfur oil-gas field in petroleum industry provides H-resistance not only for steel products, but also for rubber products2The performance requirements of S. High temperature and high pressure H in the production process of high sulfur-containing oil and gas fields2S/CO2The working condition can cause strong erosion to the rubber sealing material, especially H2S is more likely to cause sealing failure due to strong corrosion, resulting in H2S major safety accidents of natural gas leakage. H2The abundant existence of S becomes a technical bottle for restricting the effective development of high-sulfur-content oil and gas reservoirsOne of the necks. The sulfur tolerance of important equipment in oil and gas field exploitation directly determines the ability to work in a hydrogen sulfide environment.
Among a plurality of rubber sealing materials, the tetrapropylene fluoride rubber has certain heat resistance and hydrogen sulfide resistance, is usually used as a sealing material for underground equipment of a high-sulfur-content oil and gas field, but the hydrogen sulfide resistance is greatly influenced by a matching system, and a general formula cannot obtain a rubber material with high hydrogen sulfide resistance. For example, the invention patent named as "an oil-resistant and aging-resistant modified tetrapropylene fluorocarbon rubber material" (application number 201510505205.X, publication number CN 105111636A) provides a rubber material, which comprises the following components in parts by weight: 70-85 parts of tetrapropylene fluoride rubber, 5-10 parts of butadiene rubber, 10-20 parts of organosilicon-acrylate rubber, 1-2.8 parts of zinc stearate, 0.5-1.5 parts of zinc oxide, 1-3.5 parts of stearic acid, 3-8 parts of tin dioxide, 5-25 parts of modified starch, 20-45 parts of modified nano calcium carbonate, 0.9-2 parts of sulfur, 3-5 parts of dicumyl peroxide, 0.5-2 parts of benzoyl peroxide, 1.2-1.9 parts of octavinyl silsesquioxane, 0.3-0.9 part of zinc diisopropyl dithiophosphate, 0.2-0.8 part of sulfolene, 3-6 parts of an anti-aging agent and 3-12 parts of a plasticizer; wherein the modified starch is prepared according to the following process: adding starch and potassium hydroxide into water, stirring for reaction, sequentially adding carbon disulfide and hydrogen peroxide, stirring, standing and separating to obtain the modified starch. The rubber material takes the tetrapropylene fluoride rubber as a main material, and aims to provide an oil-resistant and aging-resistant modified tetrapropylene fluoride rubber material without recording of hydrogen sulfide resistance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a rubber composition for resisting hydrogen sulfide corrosion in an oil and gas field, which comprises the following components in parts by mass: 100 parts of main material, 1-2 parts of processing aid, 2-6 parts of cross-linking agent, 1.5-4 parts of anti-aging agent, 20-80 parts of reinforcing filler, 2-20 parts of sulfur-resistant agent, 2-8 parts of auxiliary cross-linking agent and 2-5 parts of flow modifier;
the main material is tetrafluoroethylene-propylene rubber;
the processing aid is sodium stearate;
the cross-linking agent is organic peroxide and dicumyl peroxide;
the anti-aging agent is 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer;
the reinforcing filler is carbon black;
the sulfur-resistant agent is a carbon nano tube;
the auxiliary crosslinking agent is triallyl cyanurate or triallyl isocyanurate;
the flow modifier is coumarone or phthalate.
The above technical solution can be further optimized as follows:
the fluorine content of the tetrapropylene fluoride rubber is 54.8-58.3%.
The carbon black is soft carbon black.
The model of the soft carbon black is N550.
The carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube.
The single-walled carbon nanotube is a chiral nanotube or a non-chiral nanotube.
The multi-walled carbon nanotube is a chiral nanotube or a non-chiral nanotube.
The achiral nanotubes are armchair nanotubes or zigzag nanotubes.
The pipe diameter of the armchair-type nanotube is 0.6-3 nm.
The purity of the sodium stearate is more than 99%.
Compared with the prior art, the invention mainly has the following beneficial technical effects:
1. the rubber composition obtained by reasonably composing the tetrapropylene fluoride rubber serving as the main material has excellent comprehensive performance and outstanding hydrogen sulfide corrosion resistance, and can be successfully used in the oil-gas well environment with the temperature of 150 ℃, the pressure of 70MPa and the partial pressure of hydrogen sulfide of 15 MPa.
2. The carbon nano tube is used as the sulfur-resistant agent, the combination of the carbon nano tube and the tetrapropylene fluoride rubber enables the rubber composition to have excellent hydrogen sulfide corrosion resistance, and the formula can be flexibly changed according to different sulfur contents of different oil and gas fields to meet different sulfur resistance requirements.
3. The invention uses organic peroxide as a crosslinking agent, uses carbon black as a reinforcing filler, and is matched with a proper auxiliary crosslinking agent and a proper flow modifier, thereby effectively improving the comprehensive performance of the rubber composition.
4. The effect of the invention is verified reliably, which has good popularization value, and the product can be used in equipment containing hydrogen sulfide gas corrosion, especially oil-gas field exploitation equipment containing hydrogen sulfide corrosion medium.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
This example describes comparative experimental conditions for the hydrogen sulfide resistance of rubber compositions of different types of carbon nanotubes. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropylene fluororubber, 1 part of sodium stearate, 2 parts of dicumyl peroxide, 1.5 parts of 2, 2, 4-trimethyl 1, 2-dihydroquinoline polymer, 35 parts of N550 type carbon black, 10 parts of carbon nano tubes, 8 parts of triallyl cyanurate and 2 parts of coumarone. The carbon nanotubes are single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs), the sizes of the single-walled carbon nanotubes and the multi-walled carbon nanotubes are all 3nm, and armchair type nanotubes are adopted. At a temperature of 100 ℃, a gas phase composition of 15MPa is 20% H2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 1. As can be seen from Table 1, the rubber composition with single-walled carbon nanotubes (SWCNTs) added thereto has lower tensile strength and elongation at break after corrosion than those with multi-walled carbon nanotubes (MWCNTs) added thereto and those without carbon nanotubes added thereto, and the rubber composition with single-walled carbon nanotubes (SWCNTs) added thereto has higher mechanical properties before and after corrosion, and has lower mass change rate and volume change rate. Multi-walled carbon nanotubes (MWCNTs) have more defects, resulting in a reduced conjugation effect, and therefore have poorer sulfur resistance than single-walled carbon nanotubes (SWCNTs). In a word, the rubber composition with the carbon nano tubes has better hydrogen sulfide corrosion resistance than the rubber composition without the carbon nano tubes, and particularly, the rubber composition with the single-walled carbon nano tubes (SWCNTs) has more obvious hydrogen sulfide corrosion resistance.
TABLE 1 data before and after Corrosion of different types of carbon nanotube rubber compositions
Example 2
This example describes comparative experimental conditions for the hydrogen sulfide resistance of rubber compositions of different types of single-walled carbon nanotubes. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropylene fluororubber, 1.5 parts of sodium stearate, 4 parts of dicumyl peroxide, 2 parts of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 35 parts of N550 type carbon black, 10 parts of single-wall carbon nanotubes, 2 parts of triallyl cyanurate and 3.5 parts of coumarone. The single-walled carbon nanotubes are represented by armchair nanotubes (armchair nanotubes), zigzag nanotubes (zigzag nanotubes), and chiral nanotubes (chiral nanotubes). At a temperature of 100 ℃, a gas phase composition of 15MPa is 20% H2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 2. As can be seen from Table 2, the rubber composition containing armchair type nanotubes (armchair nanotubes) has small variation in tensile strength, elongation at break, 100% elongation at break, and good sulfur resistance; the rubber composition containing zigzag nanotubes (zigzag nanotubes) and the rubber composition containing chiral nanotubes (chiral nanotubes) were not very different from each other and had similar sulfur resistance.
TABLE 2 data of different types of single-walled carbon nanotube rubber compositions before and after corrosion
Example 3
This example describes comparative experimental conditions of the hydrogen sulfide resistance of rubber compositions of armchair-type single-walled carbon nanotubes of different sizes. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropylene fluororubber, 1.5 parts of sodium stearate, 6 parts of dicumyl peroxide, 3 parts of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 35 parts of N550 type carbon black, 10 parts of single-walled carbon nanotube,5 parts of triallyl cyanurate and 5 parts of coumarone. The single-walled carbon nanotubes (SWCNTs) are all armchair carbon nanotubes, and the tube diameters of the nanotubes are 0.6nm, 2nm and 3nm respectively. At a temperature of 100 ℃, a gas phase composition of 15MPa is 20% H2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 3. As can be seen from Table 3, the rubber composition containing the armchair-type nanotubes with the smaller size has the better reinforcing effect, and the rubber composition containing the armchair-type nanotubes with the 0.6nm size has the elongation at break lower than that of the rubber composition containing the armchair-type nanotubes with the 2nm and 3nm sizes, but the size of the armchair-type nanotubes has little influence on the sulfur resistance, and the armrest-type nanotubes have the better sulfur resistance. Therefore, the size of the armchair-type single-walled carbon nanotube added into the rubber composition with hydrogen sulfide corrosion resistance can be between 0.6nm and 3 nm.
TABLE 3 data of armchair-type single-walled carbon nanotube rubber compositions of different sizes before and after corrosion
Example 4
This example describes comparative experiments of the hydrogen sulfide resistance of rubber compositions of armchair-type single-walled carbon nanotubes in different amounts. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropylene fluororubber, 1.5 parts of sodium stearate, 2 parts of dicumyl peroxide, 4 parts of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 35 parts of N550 type carbon black, 2 parts, 10 parts and 20 parts of single-wall carbon nanotubes, 8 parts of triallyl isocyanurate and 2 parts of phthalate. The single-walled carbon nanotubes (SWCNTs) are all armchair nanotubes. At a temperature of 100 ℃ a gas phase composition of 20% H at 15MPa2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 4. As can be seen from Table 4, the amount of the armchair-type nanotubes is small, the electron conjugated structure is too small, and the number of absorbed electrons is not large, so that the number of free radicals in the aging process of the rubber composition can not be effectively reduced; the armchair-type nanotubes are used in a large amount, and the elongation at break of the rubber composition is reduced obviously, so that the single-walled carbon nanotubes are in the rubber componentThe hydrogen sulfide resistance is preferably achieved when the amount of the compound is 2 to 20 parts by mass.
TABLE 4 data of armchair-type single-walled carbon nanotube rubber compositions before and after corrosion at different dosages
Example 5
This example describes comparative experimental conditions of the hydrogen sulfide resistance of rubber compositions of multi-walled carbon nanotubes of different sizes of armchairs. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropyl fluororubber, 1.5 parts of sodium stearate, 4 parts of dicumyl peroxide, 2 parts of 2, 2, 4-trimethyl 1, 2-dihydroquinoline polymer, 35 parts of N550 type carbon black, 10 parts of multi-wall carbon nano tubes, 2 parts of triallyl isocyanurate and 3.5 parts of phthalic acid ester. The multi-walled carbon nanotubes (MWCNTs) are all armchair nanotubes, and the sizes of the nanotubes are 3nm, 30nm and 60nm respectively. At a temperature of 100 ℃, a gas phase composition of 15MPa is 20% H2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 5. As can be seen from Table 5, the larger the size of the armchair-type multi-walled carbon nanotube, the larger the mass change rate and the volume change rate of the rubber composition after corrosion, and the poorer the sulfur resistance, indicating that the larger the size, the more defects of the multi-walled carbon nanotube are, and the reduced the conjugation effect is.
TABLE 5 data of Armrest chair type multiwall carbon nanotube rubber compositions of different dimensions before and after Corrosion
Example 6
This example describes comparative experimental conditions for the hydrogen sulfide resistance of rubber compositions compared to the hydrogen sulfide resistance of various reinforcing filler levels. The rubber composition comprises the following components in parts by mass: 100 parts of tetrapropylene fluororubber, 2 parts of sodium stearate, 6 parts of dicumyl peroxide, 3 parts of 2, 2, 4-trimethyl 1, 2-dihydroquinoline polymer and 20 parts and 60 parts of N550 type carbon black respectively80 parts of carbon nano tube, 10 parts of triallyl isocyanurate and 5 parts of phthalic acid ester. At a temperature of 100 ℃, a gas phase composition of 15MPa is 20% H2S、5%CO2And 75% CH4The results after 4 days of etching are shown in Table 6. As seen from Table 6, as the amount of N550 type carbon black was increased, the tensile strength of the rubber composition before corrosion was remarkably increased and the elongation at break was simultaneously decreased; the smaller the mass change rate and the volume change rate after corrosion, the better the sulfur resistance. The amount of the N550 type carbon black is reasonably selected according to actual conditions.
TABLE 6 data of rubber compositions with different amounts of reinforcing fillers before and after corrosion
For a better understanding of the present invention, the basic principle of the present invention will now be briefly described as follows:
the fluorine content of the tetrapropylene fluororubber used in the rubber composition of the invention is 54.8-58.3%, and the fluororubber has good hydrogen sulfide resistance and good processability, such as Aflas100S manufactured by Ruison corporation of Japan and TP-2 manufactured by Sanaifu (3F) corporation of Shanghai. The molecular chain of the rubber has no double bond, so that the rubber can only adopt a free radical crosslinking mode initiated by peroxide to form a C-C crosslinking bond with higher bond energy and excellent heat resistance and has better hydrogen sulfide resistance. The cross-linking agent is cheap and easily available dicumyl peroxide (DCP) with high efficiency, and the dicumyl peroxide (DCP) is preferably 2-6 parts by mass based on 100 parts by mass of the tetrapropylene fluoride rubber; excessive amounts of peroxide are not preferred because excessive amounts of peroxide adversely affect the properties of the final product and the decomposed residue of peroxide affects the hydrogen sulfide resistance of the tetrapropylene fluororubber, which results in a phenomenon of less crosslinking, so that it is necessary to add an auxiliary crosslinking agent such as triallyl cyanurate (TAC) or triallyl isocyanurate (TAIC) to further improve the crosslinking efficiency.
The manufacturing of the packer rubber cylinder generally adopts an injection molding method, which requires the rubber compound to have better fluidity, and the rubber cylinder generally requires higher hardness and tensile strength for better sealing performance, so a large amount of carbon black reinforcement is required, and the fluidity of the rubber compound is reduced. Therefore, in order to solve the problem of the reduction of the flow property of the rubber compound caused by carbon black reinforcement, the invention adds coumarone or phthalate as a plasticizer, thereby improving the flow property of the rubber compound.
The carbon nanotubes are divided into single-walled carbon nanotubes and multi-walled carbon nanotubes, which have three types, namely: armchair nanotubes (armchair nanotubes), zigzag nanotubes (zigzag nanotubes), and chiral nanotubes (chiral nanotubes). The armchair-type single-walled carbon nanotubes are metallic, have the most stable structure and have stronger conjugation capability. As carbon atoms in the carbon nano tube are hybridized by SP2, compared with SP3 hybridization, the S track component in SP2 hybridization is larger, so that the carbon nano tube has high modulus and high strength, the carbon nano tube also has the characteristics of large length-diameter ratio, large specific surface and small tube diameter, and the carbon nano tube has excellent mechanical property due to structural superiority and can be used as a reinforcing filler. The C-C bond in the carbon nano tube has better hydrogen sulfide resistance, and P electrons of carbon atoms on the carbon nano tube form a large-range delocalized pi-bond electron conjugated structure, so that the conjugated effect is remarkable, the electrons can be absorbed, and the number of free radicals in the rubber aging process can be effectively reduced.
The concrete process of the mixing is not particularly limited, and the mixing process and the mixing equipment commonly used in the current rubber processing process can be adopted to completely and uniformly disperse the components except the tetrapropylene fluoroelastomers in the tetrapropylene fluoroelastomers, so that the composition of the mixed rubber is uniform and consistent, and the consistency and the stability of the performance of the tetrapropylene fluoroelastomers are ensured. In the specific implementation process of the invention, the mixing is completed on an open mill, the temperature of two rollers of the open mill is controlled below 35 ℃ by refluxing water, the mixture is thinly passed (mixing raw rubber and auxiliary agent), and triangular bags are packed for 13-17 times to obtain the mixed rubber. The vulcanization process of the present invention is not particularly limited, as long as the tetrapropylene fluoride rubber can be crosslinked with each other by the crosslinking agent and the like to form a network structure. The tetrafluoroethylene-propylene rubber product can be used in oil-gas well environments with the temperature of 150 ℃, the pressure of 70MPa and the partial pressure of hydrogen sulfide of 15 MPa.
And fifthly, the rubber composition is prepared into products for oil and gas fields, the products can work in the oil and gas underground environment, the excellent sulfur resistance is kept, the complete rubber characteristic is still kept after a period of time, the performance is good, and the mining and use requirements of the oil and gas fields are met.
Sodium stearate is used as a processing aid, and the purity is required to be more than 99% so as to fully exert good performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields is characterized by comprising the following components in parts by mass: 100 parts of main material, 1-2 parts of processing aid, 2-6 parts of cross-linking agent, 1.5-4 parts of anti-aging agent, 20-80 parts of reinforcing filler, 2-20 parts of sulfur-resistant agent, 2-8 parts of auxiliary cross-linking agent and 2-5 parts of flow modifier;
the main material is tetrafluoroethylene-propylene rubber;
the processing aid is sodium stearate;
the cross-linking agent is organic peroxide and dicumyl peroxide;
the anti-aging agent is 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer;
the reinforcing filler is carbon black;
the sulfur-resistant agent is a carbon nano tube;
the auxiliary crosslinking agent is triallyl cyanurate or triallyl isocyanurate;
the flow modifier is coumarone or phthalate.
2. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 1, wherein the fluorine content of the tetrapropylene fluoride rubber is 54.8% -58.3%.
3. The rubber composition for oil and gas field corrosion resistance according to claim 1, wherein the carbon black is soft carbon black.
4. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 3, wherein the soft carbon black is N550.
5. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
6. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 5, wherein the single-walled carbon nanotube is chiral nanotube or achiral nanotube.
7. The hydrogen sulfide corrosion resistant rubber composition for oil and gas fields according to claim 5, wherein the multi-walled carbon nanotubes are chiral nanotubes or achiral nanotubes.
8. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 6 or 7, wherein the achiral nanotubes are armchair nanotubes or zigzag nanotubes.
9. The rubber composition for resisting hydrogen sulfide corrosion in oil and gas fields as claimed in claim 8, wherein the tube diameter of the armchair-type single-walled carbon nanotube is 0.6-3 nm.
10. The rubber composition for oil and gas field corrosion resistance according to claim 1, wherein the purity of the sodium stearate is above 99%.
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| CN102250437A (en) * | 2011-06-29 | 2011-11-23 | 中国石油大学(北京) | Acidproof, alkali-proof and hydrogen-sulphide-corrosion-resistant aflas composite |
| CN109721898A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | 4 third fluorine vulcanizates of one kind and preparation method thereof |
| CN110157124A (en) * | 2019-05-10 | 2019-08-23 | 上海杜实新材料科技有限公司 | A kind of tetrapropanate fluorine rubber composition of hydrogen sulfide corrosion-resistant and its application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250437A (en) * | 2011-06-29 | 2011-11-23 | 中国石油大学(北京) | Acidproof, alkali-proof and hydrogen-sulphide-corrosion-resistant aflas composite |
| CN109721898A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | 4 third fluorine vulcanizates of one kind and preparation method thereof |
| CN110157124A (en) * | 2019-05-10 | 2019-08-23 | 上海杜实新材料科技有限公司 | A kind of tetrapropanate fluorine rubber composition of hydrogen sulfide corrosion-resistant and its application |
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