CN109233775B - Removing agent for sulfur-containing peculiar smell gas of heavy oil thermal production well and preparation method thereof - Google Patents
Removing agent for sulfur-containing peculiar smell gas of heavy oil thermal production well and preparation method thereof Download PDFInfo
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- CN109233775B CN109233775B CN201811119603.8A CN201811119603A CN109233775B CN 109233775 B CN109233775 B CN 109233775B CN 201811119603 A CN201811119603 A CN 201811119603A CN 109233775 B CN109233775 B CN 109233775B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
- C09K8/532—Sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/20—Hydrogen sulfide elimination
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Abstract
The invention belongs to the technical field of chemical agents for oil fields and preparation, and particularly relates to a remover for sulfur-containing peculiar smell gas of a heavy oil thermal production well and a preparation method thereof. The remover is prepared by reacting triazine substances, peroxide and a metal complexing agent in a reaction medium, wherein the triazine substances are 1, 3, 5-trihydroxyethyl hexahydro-s-triazine or 1, 3, 5-trialkyl hexahydro-s-triazine, and the peroxide is one of hydrogen peroxide, peracetic acid, carbamide peroxide and sodium percarbonate. The remover has low pH value, so the problem of scaling of a casing, an oil pipe and a shaft of an oil well can not be caused; the remover of the invention can effectively remove H2S, the odor caused by hydrogen sulfide can be effectively removed, and the odor generated by mercaptan and carbonyl sulfide can be effectively removed; meanwhile, the removing agent has less dosage which can be reduced by more than 50% compared with the common medicament, and can be used for H of oil well produced liquid2The removal rate of S, mercaptan and carbonyl sulfide reaches 100 percent.
Description
Technical Field
The invention belongs to the technical field of chemical agents for oil fields and preparation, and particularly relates to a remover for sulfur-containing peculiar smell gas of a heavy oil thermal production well and a preparation method thereof.
Background
China has rich thickened oil resources, and the application scale is increased year by using thickened oil thermal recovery as an effective means for thickened oil, super thickened oil and extra super thickened oil. During the heavy oil huff-puff and thermal flooding process by adopting high-temperature hot steam, sulfur-containing compounds in crude oil can generate a series of hydrothermal cracking reactions to generate odorous sulfur-containing compounds such as hydrogen sulfide, methyl mercaptan, ethanethiol, carbonyl sulfide, thioether and the like, especially ultra-heavy oil is injected with steam, after being stewed for a period of time, a large amount of water vapor is generated at the initial stage of open flow, the steam contains a large amount of sulfur-containing compounds such as hydrogen sulfide, methyl mercaptan, ethanethiol and the like, and the content of hydrogen sulfide (containing certain methyl mercaptan and ethanethiol) in associated gas of a thermal production well of a victory oil field reaches 32000-50000 mg/m-3The odor in the well site and the surrounding environment of single well oil pumping is serious, and the life safety and health of operating personnel are seriously threatened.
Currently, the adopted desulfurizing agents such as triazines, alcamines, aldehydes and the like are generally added through a sleeve pipe, and are fully mixed and reacted in an oil pipe, so that although the peculiar smell caused by hydrogen sulfide can be removed, the peculiar smell generated by mercaptan, carbonyl sulfide and the like is difficult to eliminate. And triazine and alcamines have high alkalinity, and are easy to cause the scaling of oil well casings and oil pipes.
In order to solve the problem of scaling, the pH value of the triazine desulfurizer is adjusted to be low, or the triazine desulfurizer is matched with an anti-scaling agent for use. As the decomposition speed of the triazine is accelerated along with the reduction of the pH value, the effect of the medicament is reduced along with the prolonging of the storage period.
Disclosure of Invention
The invention provides a remover for sulfur-containing peculiar smell gas of a heavy oil thermal production well and a preparation method thereof aiming at the defects of the prior art. The remover of the invention can remove the main sulfur compounds such as hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the oil well produced fluid, and can not cause the scaling of an oil well system.
The invention provides a remover for sulfur-containing peculiar smell gas of a heavy oil thermal production well, which is formed by reacting triazine substances, peroxide and a metal complexing agent in a reaction medium, wherein the molecular structural formula of the remover is one or more of the following formulas (1), (2) and (3):
the invention provides a preparation method of a remover for sulfur-containing stink gas of a heavy oil thermal production well, which comprises the following specific steps:
(1) adding a reaction medium, a triazine substance and a metal complexing agent into a three-mouth bottle in sequence, and then fixing the three-mouth bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 60-180rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature of a temperature controller to be 30-70 ℃;
(4) adding peroxide into a separating funnel at the speed of 5-10 drops/min, and reacting for 0.5-1.0h after the dropping is finished to obtain the remover.
The triazine substance is 1, 3, 5-trihydroxyethyl hexahydro-s-triazine or 1, 3, 5-trialkyl hexahydro-s-triazine.
The peroxide is one of hydrogen peroxide, peracetic acid, carbamide peroxide and sodium percarbonate.
The metal complexing agent is one of an ammonia hydroxyl complexing agent and a sulfhydryl complexing agent.
The reaction medium is water or low molecular alcohol.
The adding molar ratio of the triazine substance, the peroxide, the metal complexing agent and the reaction medium is 1:1-3:0.01-0.03: 8-10.
The temperature controller controls the temperature to be 55-60 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the remover has low pH value, so the problem of scaling of a casing, an oil pipe and a shaft of an oil well can not be caused;
(2) the remover of the invention can effectively remove H2The odor caused by the S hydrogen sulfide can be effectively removed, and the odor generated by mercaptan and carbonyl sulfide can be effectively removed.
(3) The remover disclosed by the invention is strong in stability, can be stored for a long time, and does not have the problem that the effect of the medicament is reduced along with the prolonging of the storage period.
(4) The invention has less dosage of the remover, which can reduce the dosage by more than 50 percent compared with the dosage of the common medicament and can treat H of oil well produced liquid2The removal rate of S, mercaptan and carbonyl sulfide reaches 100 percent.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1
(1) Adding reaction medium water, 1, 3, 5-trihydroxyethyl hexahydro-s-triazine and an ammonia hydroxyl complexing agent into a three-necked bottle in sequence, and then fixing the three-necked bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 60rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature by a temperature controller to be 30 ℃;
(4) adding peroxide hydrogen peroxide into a separating funnel at the speed of 5 drops/min, and reacting for 0.5h after the dropping is finished to obtain a remover A1。
The molar ratio of the added 1, 3, 5-trihydroxyethyl hexahydro-s-triazine to the added hydrogen peroxide to the added ammonia-hydroxyl complexing agent to the added water is 1:1:0.01: 8.
The remover A1The molecular structural formula of (A) is as follows:
oil well B of certain block of oil extraction plant of victory oil field island12Oil well liquid production volume 85m3D, the content of wellhead hydrogen sulfide is 300ppm, the content of methyl mercaptan is 60ppm, the content of ethanethiol is 35ppm, the content of carbonyl sulfur is 20ppm, 30kg/d of triazine desulfurizer and the remover A prepared by the invention are respectively used1The effect of the treatment at 12kg/d is shown in Table 1.
TABLE 1 triazine sweetening agent and remover A1To B12Results of well head off-flavor gas treatment
From Table 1 it can be seen that the stripping agent A1The consumption of the triazine desulfurizer is reduced by 60 percent, and the content of hydrogen sulfide, the content of methyl mercaptan, the content of ethanethiol and the content of carbonyl sulfide in the off-flavor gas after the triazine desulfurizer is treated is 18ppm, 52ppm, 33ppm and 16 ppm; removing agent A1The contents of hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the treated off-flavor gases are all 0. Removing agent A1Compared with triazine desulfurizer, the usage amount is greatly reduced, and the effect of treating off-flavor gas is more obvious.
Example 2
(1) Adding reaction medium water, triazine substance 1, 3, 5-trihydroxyethyl hexahydro-s-triazine and metal complexing agent sulfhydryl complexing agent into a three-necked bottle in sequence, and fixing the three-necked bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 80rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature by a temperature controller to be 40 ℃;
(4) peroxide peracetic acid is added into a separating funnel at the speed of 6 drops/min, and the dropping is finishedPost-reaction for 0.6h to obtain remover A2。
The molar ratio of the added 1, 3, 5-trihydroxyethyl hexahydro-s-triazine, peroxyacetic acid, a mercapto complexing agent and water is 1:1.5:0.02: 9.
The remover A2The molecular structural formula of (A) is as follows:
oil well B in certain block of oil extraction plant of victory oil field island15Oil well liquid production 120m3600ppm of wellhead hydrogen sulfide, 130ppm of methyl mercaptan, 40ppm of ethanethiol and 30ppm of carbonyl sulfide, and respectively using 50kg/d of triazine desulfurizer and remover A prepared by the invention2The treatment was carried out at 22kg/d, and the results are shown in Table 2.
TABLE 2 triazine sweetening agent and remover A2To B15Results of well head off-flavor gas treatment
From Table 2 it can be seen that the stripping agent A2The consumption of the triazine desulfurizer is reduced by 56 percent, and the content of hydrogen sulfide, the content of methyl mercaptan, the content of ethanethiol and the content of carbonyl sulfide in the off-flavor gas after the triazine desulfurizer is treated is 25ppm, 122ppm, 35ppm and 27 ppm; removing agent A2The contents of hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the treated off-flavor gases are all 0. Removing agent A2Compared with triazine desulfurizer, the usage amount is greatly reduced, and the effect of treating off-flavor gas is more obvious.
Example 3
(1) Adding reaction medium low molecular alcohol, triazine substance 1, 3, 5-trihydroxyethyl hexahydro-s-triazine and metal complexing agent ammonia-hydroxyl complexing agent into a three-necked bottle in sequence, and fixing the three-necked bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 100rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature by a temperature controller to be 55 ℃;
(4) adding carbamide peroxide into a separating funnel at the speed of 7 drops/min, and reacting for 0.7h after the dropping is finished to obtain remover A3。
The adding molar ratio of the 1, 3, 5-trihydroxyethyl hexahydro-s-triazine, the carbamide peroxide, the ammine hydroxyl complexing agent and the low molecular alcohol is 1:2.0:0.03: 10.
The remover A3The molecular structural formula of (A) is as follows:
oil well B in certain block of oil extraction plant of victory oil field island21Oil well fluid production rate of 150m3The content of wellhead hydrogen sulfide is 1000ppm, the content of methyl mercaptan is 150ppm, the content of ethanethiol is 60ppm, the content of carbonyl sulfur is 20ppm, 80kg/d of triazine desulfurizer and the remover A prepared by the invention are respectively used330kg/d were treated, and the results are shown in Table 3.
TABLE 3 triazine sweetening agent and remover A3To B21Results of well head off-flavor gas treatment
From Table 3 it can be seen that the stripping agent A3The consumption of the triazine desulfurizer is reduced by 62.5 percent, and the hydrogen sulfide content, the methyl mercaptan content, the ethyl mercaptan content and the carbonyl sulfide content of the off-flavor gas after the triazine desulfurizer is treated are 45ppm, 135ppm, 52ppm and 18ppm respectively; removing agent A3The contents of hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the treated off-flavor gases are all 0. Removing agentA3Compared with triazine desulfurizer, the usage amount is greatly reduced, and the effect of treating off-flavor gas is more obvious.
Example 4
(1) Adding reaction medium water, triazine substance 1, 3, 5-trialkyl hexahydro-s-triazine and metal complexing agent sulfydryl complexing agent into a three-necked bottle in sequence, and fixing the three-necked bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 120rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature by a temperature controller to be 60 ℃;
(4) adding peroxide sodium percarbonate into a separating funnel at the speed of 8 drops/min, and reacting for 0.9h to obtain remover A4。
The molar ratio of the 1, 3, 5-trialkyl hexahydro-s-triazine to the sodium percarbonate to the added mercapto complexing agent to the added water is 1:2.5:0.02: 9.
The remover A4The molecular structural formula of (A) is as follows:
oil well C in certain block of oil production plant of Shangli oilfield2Oil well liquid production 120m3The content of wellhead hydrogen sulfide is 1500ppm, the content of methyl mercaptan is 250ppm, the content of ethanethiol is 80ppm, the content of carbonyl sulfur is 60ppm, 100kg/d of triazine desulfurizer and the remover A prepared by the invention are respectively used445kg/d were treated, and the results are shown in Table 4.
TABLE 4 triazine sweetening agent and remover A4To C2Results of well head off-flavor gas treatment
As can be seen from Table 4Removing agent A4The consumption of the triazine desulfurizer is reduced by 55 percent, and the hydrogen sulfide content, the methyl mercaptan content, the ethyl mercaptan content and the carbonyl sulfide content of the off-flavor gas after the triazine desulfurizer is treated are 52ppm, 185ppm, 63ppm and 45ppm respectively; removing agent A4The contents of hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the treated off-flavor gases are all 0. Removing agent A4Compared with triazine desulfurizer, the usage amount is greatly reduced, and the effect of treating off-flavor gas is more obvious.
Example 5
(1) Sequentially adding reaction medium low molecular alcohol, 1, 3, 5-trialkyl hexahydro-s-triazine as triazine substances and an ammonia-hydroxyl complexing agent as a metal complexing agent into a three-necked bottle, and then fixing the three-necked bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 180rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature by a temperature controller to be 70 ℃;
(4) adding peroxide hydrogen peroxide into a separating funnel at the speed of 10 drops/min, and reacting for 1.0h after the dropping is finished to obtain a remover A5。
The molar ratio of the added 1, 3, 5-trialkyl hexahydro-s-triazine to the added hydrogen peroxide to the added ammonia-hydroxyl complexing agent to the added low molecular alcohol is 1:3.0:0.03: 10.
The remover A5The molecular structural formula of (A) is as follows:
oil well C in certain block of oil production plant of Shangli oilfield5Oil well liquid production 180m3The content of wellhead hydrogen sulfide is 2000ppm, the content of methyl mercaptan is 420ppm, the content of ethanethiol is 130ppm, the content of carbonyl sulfur is 70ppm, 150kg/d of triazine desulfurizer and the remover A prepared by the invention are respectively used560kg/d were treated, and the results are shown in Table 5.
TABLE 5 triazinesDesulfurizing agent and removing agent A5To C5Results of well head off-flavor gas treatment
From Table 5 it can be seen that the stripping agent A5The consumption of the triazine desulfurizer is reduced by 60 percent, and the content of hydrogen sulfide, the content of methyl mercaptan, the content of ethanethiol and the content of carbonyl sulfide in the off-flavor gas after the triazine desulfurizer is treated is 25ppm, 312ppm, 98ppm and 57 ppm; removing agent A5The contents of hydrogen sulfide, methyl mercaptan, ethyl mercaptan and carbonyl sulfide in the treated off-flavor gases are all 0. Removing agent A5Compared with triazine desulfurizer, the usage amount is greatly reduced, and the effect of treating off-flavor gas is more obvious.
Claims (7)
1. A preparation method of a remover for sulfur-containing peculiar smell gas of a thick oil thermal production well is characterized by comprising the following specific steps:
(1) adding a reaction medium, a triazine substance and a metal complexing agent into a three-mouth bottle in sequence, and then fixing the three-mouth bottle on an electric heating sleeve with a magnetic stirrer;
(2) putting a magnetic rotor into the three-mouth bottle, and then respectively installing a temperature controller and a separating funnel into the three-mouth bottle;
(3) starting magnetic stirring, wherein the stirring speed is 60-180rpm, heating the substances in the three-necked bottle by an electric heating sleeve, and controlling the temperature of a temperature controller to be 30-70 ℃;
(4) adding peroxide into a separating funnel at the speed of 5-10 drops/min, and reacting for 0.5-1.0h after the dropping is finished to obtain a remover;
the triazine substance is 1, 3, 5-trihydroxyethyl hexahydro-s-triazine or 1, 3, 5-trialkyl hexahydro-s-triazine.
2. The preparation method according to claim 1, wherein the peroxide is one of hydrogen peroxide, peracetic acid, carbamide peroxide and sodium percarbonate.
3. The process according to claim 1, wherein the reaction medium is water or a low molecular alcohol.
4. The method according to claim 1, wherein the metal complexing agent is one of an ammine hydroxyl complexing agent and a mercapto complexing agent.
5. The process according to claim 1, wherein the triazine, the peroxide, the metal complexing agent and the reaction medium are added in a molar ratio of 1:1 to 3:0.01 to 0.03:8 to 10.
6. The method of claim 1, wherein the temperature controller controls the temperature to be 55-60 ℃.
7. The removing agent obtained by the production process according to any one of claims 1 to 6, wherein the molecular structural formula of the removing agent is one or more of the following formulae (1), (2) and (3):
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| CN109772104B (en) * | 2019-02-20 | 2021-07-20 | 中国海洋石油集团有限公司 | Hydrogen sulfide absorbent for acid washing and use method thereof |
| CN109913282B (en) * | 2019-03-27 | 2020-11-03 | 陕西森瑞石油技术开发有限公司 | Ultralow-temperature organic composite sulfur removal agent for gas field |
| CN114058420B (en) * | 2021-11-13 | 2022-10-28 | 山东省众力环保科技有限公司 | Hydrogen sulfide remover for oil and gas wells and preparation method thereof |
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