CN109971447B - Bactericidal corrosion inhibitor for oil well gathering and transporting and sewage treatment system and preparation method thereof - Google Patents
Bactericidal corrosion inhibitor for oil well gathering and transporting and sewage treatment system and preparation method thereof Download PDFInfo
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- CN109971447B CN109971447B CN201910359759.1A CN201910359759A CN109971447B CN 109971447 B CN109971447 B CN 109971447B CN 201910359759 A CN201910359759 A CN 201910359759A CN 109971447 B CN109971447 B CN 109971447B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/147—Nitrogen-containing compounds containing a nitrogen-to-oxygen bond
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
Abstract
The invention belongs to the technical field of oilfield production, and particularly relates to a sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system and a preparation method thereof. The bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system comprises the following raw materials: the main sterilizing and corrosion inhibiting agent is hydroxyl-containing quaternary ammonium salt. The sterilization type corrosion inhibitor is not only to CO2/H2S acidic Medium and Cl‑The corrosion caused by the corrosion has good inhibition effect, and has good sterilization and bacteriostasis effects on common SRB, TGB, FB and other bacteria in oil fields, and the product is nontoxic, has no harm to oil layers, is simple and convenient to construct and operate, and overcomes the defects of large workload of adding single-type medicaments, difficult field implementation and management, high medicament adding cost, incompatibility and the like.
Description
Technical Field
The invention belongs to the technical field of oilfield production, and particularly relates to a sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system and a preparation method thereof.
Background
Oilfield production accessIn the middle and later period, the water content of the oil well is continuously increased, and the oil well contains high salinity brine and acid gas CO2/H2S and the existence of bacterial microorganisms seriously affect the corrosion degree of metal pipes in an oil well gathering and transportation and sewage treatment system, wherein the existence of the bacterial microorganisms, particularly anaerobic microorganisms SRB, is easily adsorbed on the pipe wall to cause local corrosion perforation of the metal pipes.
At present, a single type of medicament is adopted as a corrosion inhibitor for medium and high salinity brine and acid gas corrosion in an oil field, and the single type of medicament does not have the effects of sterilization and bacteriostasis; the existing quaternary ammonium salt type bactericide adopted for bacterial microbial corrosion has a certain corrosion prevention effect, but an adsorption film formed on the surface of metal is not compact, so that local corrosion is easily caused. Therefore, a sterilization type corrosion inhibitor with both an anti-corrosion effect and a sterilization effect is urgently needed in an oil well gathering and transportation and sewage treatment system in oil field production to solve the field corrosion problem.
Disclosure of Invention
The invention aims to provide a sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system and a preparation method thereof aiming at the defects, wherein the sterilization type corrosion inhibitor is used for treating CO2/H2S acidic Medium and Cl-The corrosion caused by the corrosion has good inhibition effect, and has good sterilization and bacteriostasis effects on common SRB, TGB, FB and other bacteria in oil fields, and the product is nontoxic, has no harm to oil layers, is simple and convenient to construct and operate, and overcomes the defects of large workload of adding single-type medicaments, difficult field implementation and management, high medicament adding cost, incompatibility and the like.
The technical scheme of the invention is as follows: a sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system comprises the following raw materials: a main sterilizing and corrosion inhibiting agent, a synergist, an auxiliary agent and water; the main sterilization and corrosion inhibition agent is hydroxyl-containing quaternary ammonium salt, and the structural general formula of the hydroxyl-containing quaternary ammonium salt is as follows:
wherein R is phenyl or-COONa.
The bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system is prepared from the following raw materials in parts by weight: 40-50% of a main sterilizing and corrosion inhibiting agent, 5-10% of a synergist, 8-10% of an auxiliary agent and 30-45% of water.
The synergist is a mixture of sodium gluconate and thiourea, wherein the weight ratio of the sodium gluconate to the thiourea is as follows: the thiourea is 1: 1-2.
The auxiliary agent is a mixture of dodecyl dimethyl benzyl ammonium chloride and carbazone, wherein the weight ratio of dodecyl dimethyl benzyl ammonium chloride: the ratio of the kasong to the kasong is 1-3: 1.
The addition concentration of the sterilization type corrosion inhibitor is 30-100 ppm.
The preparation of the main sterilizing and corrosion inhibiting agent is as follows: firstly, adding pyridine and formaldehyde into a reactor provided with a condensation reflux device according to the molar ratio of 1: 1-3, and reacting for 4-6 hours at 90 ℃; then adding a quaternizing agent RCH dropwise2Cl, wherein pyridine: RCH2Cl is 1: 0.6-0.9, and the reaction is carried out for 4-6 h at the temperature of 90 ℃ to obtain the main sterilizing and inhibiting agent; r is phenyl and-COONa.
The reaction process is as follows:
the molar ratio of the pyridine to the formaldehyde is 1: 3; pyridine according to a molar ratio: RCH2Cl is 1: 0.9; firstly, reacting for 4 hours at 90 ℃; in the dropwise addition of a quaternizing agent RCH2After Cl, the temperature is controlled at 90 ℃ for reaction for 6 h.
The preparation method of the bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system comprises the following steps:
firstly, adding pyridine and formaldehyde into a reactor provided with a condensation reflux device according to the molar ratio of 1: 1-3, and reacting for 4-6 hours at 90 ℃; then adding a quaternizing agent RCH dropwise2Cl, wherein pyridine: RCH2Cl is 1: 0.6-0.9, and the reaction is carried out for 4-6 h at the temperature of 90 ℃ to obtain the main sterilizing and inhibiting agent;
then adding 30-45% of water and 5-10% of synergist into another reactor, stirring to completely dissolve the mixture, adding 8-10% of auxiliary agent and 40-50% of sterilization and corrosion inhibition main agent, and stirring for 30min to obtain the sterilization type corrosion inhibitor.
The invention has the beneficial effects that: the invention relates to a sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system, which firstly adopts pyridine, formaldehyde and a quaternizing agent RCH2Cl is synthesized into a main sterilization and corrosion inhibition agent, and then a synergist and an auxiliary agent are compounded to improve the sterilization and corrosion inhibition effect.
The main sterilizing and corrosion inhibiting agent is quaternary ammonium salt containing hydroxyl group, and the molecule of the main sterilizing and corrosion inhibiting agent contains active hydrogen atoms and can react with-NCO in bacteria to make antibacterial molecules become a part of macromolecules, so that the macromolecules contain antibacterial groups and have an antibacterial effect; in addition, the main agent is prepared by the quaternizing agent RCH2The quaternization of Cl has a strong stripping effect and can kill SRB growing below the clay; because molecules contain electrophilic groups such as-OH and the like, the coating has better film forming property and excellent corrosion inhibition property on the metal surface; the molecule is quaternary ammonium salt, is positively charged, can receive negative charges generated by anode ionization, inhibits the generation of cathodes, prevents corrosion from proceeding, and plays a role in inhibiting corrosion.
The synergist has a synergistic effect with the main sterilizing and corrosion inhibiting agent, the synergist is a mixture of sodium gluconate and thiourea, the sodium gluconate contains 6-OH which can form hydrogen bonds with the main sterilizing and corrosion inhibiting agent, and a large number of hydrogen bonds can thicken an adsorption layer on the metal surface to form H blocking+A barrier adjacent to the metal surface to reduce the occurrence of corrosion; secondly, the sterilization and corrosion inhibition main agent and the sodium gluconate are both in rigid annular structures, and when the sterilization and corrosion inhibition main agent and the sodium gluconate are adsorbed on the surface of metal to form a film, gaps are easy to exist due to structural characteristics, so that thiourea with a small molecular structure is required to fill up the gaps, the compactness of the adsorption film is enhanced, and the corrosion inhibition effect is improved.
The assistant and the main bactericidal and corrosion-inhibiting agent have a synergistic effect, the main bactericidal and corrosion-inhibiting agent cannot be completely dispersed in water, and a cationic surfactant dodecyl dimethyl benzyl ammonium chloride with a bactericidal effect is required to be dispersed so as to be uniformly dispersed in the water to improve the corrosion-inhibiting and bactericidal effects, and meanwhile, the addition of the kasong enhances the bactericidal effects.
The sterilization type corrosion inhibitor has the following advantages:
(1) overcomes the defects of large workload of adding single type medicament, difficult field implementation and management, high medicament adding cost, incompatibility and the like.
(2) The sterilization type corrosion inhibitor is not only to CO2/H2S acidic Medium and Cl-Has good inhibition effect on the induced corrosion, has good sterilization and bacteriostasis effects on common SRB, TGB, FB and other bacteria in the oil field,
(3) the product is nontoxic, harmless to oil layer, simple and convenient in construction operation, and reduces the investment of dosing equipment and the difficulty of field management.
(4) The corrosion inhibition and sterilization performance is improved by compounding.
(5) The main agent of the bactericidal corrosion inhibitor has simple synthesis process and high efficiency.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
The bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system is prepared from the following raw materials in parts by weight: 42% of a main sterilizing and corrosion inhibiting agent; the synergist is 10 percent, wherein the synergist is a mixture of 5 percent of thiourea and 5 percent of sodium gluconate; the auxiliary agent is 8 percent, wherein the auxiliary agent is a mixture of 5 percent of dodecyl dimethyl benzyl ammonium chloride and 3 percent of carbazone; the water content is 40%.
The main sterilization and corrosion inhibition agent is hydroxyl-containing quaternary ammonium salt, and the structural general formula of the hydroxyl-containing quaternary ammonium salt is as follows:
wherein R is phenyl or-COONa.
The preparation method of the bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system specifically comprises the following steps:
firstly, pyridine and formaldehyde are mixed according to the mole ratioAdding the mixture into a reactor provided with a condensation reflux device according to the molar ratio of 1:3, and reacting for 4 hours at the temperature of 90 ℃; then adding a quaternizing agent RCH dropwise2Cl, wherein pyridine: RCH2Cl is 1:0.9, and the main sterilizing and corrosion inhibiting agent is obtained after the reaction is carried out for 6 hours at the temperature of 90 ℃.
Adding 40% of water, 5% of thiourea and 5% of sodium gluconate into another reactor, stirring to completely dissolve the mixture, adding 5% of dodecyl dimethyl benzyl ammonium chloride, 3% of carbazone and 42% of a sterilization and corrosion inhibition main agent, and stirring for 30min to obtain the sterilization type corrosion inhibitor.
The bacterial content is measured according to standard SY/T5329-2012 recommendation index and analysis method for water quality of clastic rock reservoir water injection, and the corrosion inhibition rate and corrosion rate are measured according to standard SY/T5273-2014 evaluation method for corrosion inhibitor performance for oilfield produced water.
The bactericidal corrosion inhibitor described in the embodiment 1 is added to a Wen-I sewage treatment station of an oil production plant, and the daily treated water amount of the station is 11000m3Because the operation period is longer, the mineralization degree of sewage is high, bacteria are bred in the treatment process, in addition, acidic gases such as carbon dioxide and the like are dissolved in the sewage, the average corrosion rate is 0.1602mm/a, in 2018, a sterilization type corrosion inhibitor is added into the united station according to 100ppm, and a plunger pump is adopted to uniformly add the sterilized corrosion inhibitor into an incoming water pipeline and an external delivery port of the sewage treatment station.
After the addition for one month, the bacterial content is obviously reduced to be basically 0, the average corrosion rate after filtration after corrosion rate treatment is 0.0234mm/a, and the average corrosion inhibition rate is 85.39%.
Table 1: water quality monitoring result of Wenyi sewage treatment station
Example 2
The bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system is prepared from the following raw materials in parts by weight: 42% of a main sterilizing and corrosion inhibiting agent; the synergist is 10 percent, wherein the synergist is a mixture of 5 percent of thiourea and 5 percent of sodium gluconate; the auxiliary agent is 8 percent, wherein the auxiliary agent is a mixture of 5 percent of dodecyl dimethyl benzyl ammonium chloride and 3 percent of carbazone; the water content is 40%.
The main sterilization and corrosion inhibition agent is hydroxyl-containing quaternary ammonium salt, and the structural general formula of the hydroxyl-containing quaternary ammonium salt is as follows:
wherein R is phenyl or-COONa.
The preparation method of the bactericidal corrosion inhibitor for the oil well gathering and transporting and sewage treatment system specifically comprises the following steps:
adding pyridine and formaldehyde into a reactor provided with a condensation reflux device according to the molar ratio of 1:2, and reacting for 4 hours at the temperature of 90 ℃; then adding a quaternizing agent RCH dropwise2Cl, wherein pyridine: RCH2Cl is 1:0.6, and the main sterilizing and corrosion inhibiting agent is obtained after the reaction is carried out for 6 hours at the temperature of 90 ℃.
Adding 40% of water, 5% of thiourea and 5% of sodium gluconate into another reactor, stirring to completely dissolve the mixture, adding 5% of dodecyl dimethyl benzyl ammonium chloride, 3% of carbazone and 42% of a sterilization and corrosion inhibition main agent, and stirring for 30min to obtain the sterilization type corrosion inhibitor.
Water samples from W33-113 and NW33-66 well heads of a four-oil-extraction plant are taken, corrosion rates and bacterial changes before and after the two wells are added with the bactericidal corrosion inhibitor described in the embodiment 2 are evaluated indoors, and the chemical concentration is 50 ppm. After the implementation, the bacteria is 0, the corrosion rate is controlled to be below 0.0209mm/a, and the corrosion inhibition rate is above 80%.
Table 2: bacteria and corrosion rate comparison before and after implementation of two well water samples in four oil extraction plants
Comparative example
Taking the oil extraction four-factory-hydrologic-diplex No. 5 separator as a water sample, and performing a performance comparison experiment on the compound of the raw materials of the bactericidal corrosion inhibitor, wherein the corrosion rate of the water sample at the outlet of the separator is 0.1482mm/a and the SRB is 10 before the experiment2TGB is 103The comparison results are shown in Table 3.
Table 3: raw material compounding comparison result
Claims (8)
1. A sterilization type corrosion inhibitor for an oil well gathering and transporting and sewage treatment system is characterized by comprising the following raw materials: a main sterilizing and corrosion inhibiting agent, a synergist, an auxiliary agent and water; wherein the synergist is a mixture of sodium gluconate and thiourea; the auxiliary agent is a mixture of dodecyl dimethyl benzyl ammonium chloride and carbazone; the main sterilizing and corrosion inhibiting agent is hydroxyl-containing quaternary ammonium salt, and the structural general formula of the hydroxyl-containing quaternary ammonium salt is as follows:
wherein R is phenyl or-COONa.
2. The bactericidal corrosion inhibitor for oil well gathering and sewage treatment systems of claim 1, which is prepared from the following raw materials in parts by weight: 40-50% of a main sterilizing and corrosion inhibiting agent, 5-10% of a synergist, 8-10% of an auxiliary agent and 30-45% of water.
3. The bactericidal corrosion inhibitor for oil well gathering and sewage treatment systems according to claim 1 or 2, wherein the weight ratio of sodium gluconate: the thiourea is 1: 1-2.
4. The bactericidal corrosion inhibitor for oil well gathering and sewage treatment systems according to claim 1 or 2, wherein the addition agent comprises dodecyl dimethyl benzyl ammonium chloride: the ratio of the kasong to the kasong is 1-3: 1.
5. The bactericidal corrosion inhibitor for oil well gathering and sewage treatment systems according to claim 2, wherein the addition concentration of the bactericidal corrosion inhibitor is 30-100 ppm.
6. The preparation method of the bactericidal corrosion inhibitor for the oil well gathering and sewage treatment system according to claim 1, wherein water, the synergist, the auxiliary agent and the main bactericidal and corrosion-inhibiting agent are mixed and stirred, and the main bactericidal and corrosion-inhibiting agent is prepared by the following steps: firstly, adding pyridine and formaldehyde into a reactor provided with a condensation reflux device according to the molar ratio of 1: 1-3, and reacting for 4-6 hours at 90 ℃; then adding a quaternizing agent RCH dropwise2Cl, wherein pyridine: RCH2Cl is 1: 0.6-0.9, and the reaction is carried out for 4-6 h at the temperature of 90 ℃ to obtain the main sterilizing and inhibiting agent; r is phenyl and-COONa.
7. The method for preparing the bactericidal corrosion inhibitor for the oil well gathering and sewage treatment system as recited in claim 6, wherein the pyridine and the formaldehyde are mixed in a molar ratio of 1: 3; pyridine according to a molar ratio: RCH2Cl is 1: 0.9; firstly, reacting for 4 hours at 90 ℃; in the dropwise addition of a quaternizing agent RCH2After Cl, the temperature is controlled at 90 ℃ for reaction for 6 h.
8. The preparation method of the bactericidal corrosion inhibitor for the oil well gathering and sewage treatment system according to claim 6, wherein 30-45% of water and 5-10% of synergist are added into another reactor, stirring is carried out to completely dissolve the synergist, 8-10% of assistant is added, 40-50% of the prepared main bactericidal and corrosion-inhibiting agent is added, and stirring is carried out for 30min to obtain the bactericidal corrosion inhibitor.
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| CN111487376A (en) * | 2020-04-26 | 2020-08-04 | 西南石油大学 | Method for measuring interaction of components compounded by imidazoline derivative and corrosion inhibitor |
| CN112646558B (en) * | 2020-12-18 | 2022-08-16 | 成都劳恩普斯科技有限公司 | Ecological safety sterilization corrosion inhibitor special for shale gas pipeline and preparation method thereof |
| CN112592705B (en) * | 2020-12-22 | 2021-07-13 | 西南石油大学 | Ecological safety type scale and corrosion inhibitor and preparation method thereof |
| CN114231266B (en) * | 2021-12-31 | 2022-12-02 | 成都劳恩普斯科技有限公司 | Non-foaming sulfur-free corrosion inhibitor with sterilization performance and preparation method thereof |
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