CN112778993B - Multi-quaternary ammonium salt corrosion inhibitor and preparation method thereof - Google Patents
Multi-quaternary ammonium salt corrosion inhibitor and preparation method thereof Download PDFInfo
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- 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
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
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- 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
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- 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
- C23F11/141—Amines; Quaternary ammonium compounds
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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
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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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
- C23F11/16—Sulfur-containing compounds
Abstract
The invention provides a multi-quaternary ammonium salt corrosion inhibitor and a preparation method thereof, wherein polyamine and epoxy chloropropane are uniformly mixed and then are placed at 0-40 ℃ for reaction for 10-18h to obtain a polychlorinated substituent A; uniformly mixing the polychlorinated substituent A and a nitrogen-containing compound, placing at 90-150 ℃, and stirring for reacting for 5-8 hours to obtain a polyquaternary ammonium salt B; and mixing the polyquaternium B with ethanol, thiourea and acetic acid, and uniformly stirring to obtain the polyquaternium corrosion inhibitor. The multi-quaternary ammonium salt corrosion inhibitor has the characteristics of strong adsorption capacity, fast film forming, low corrosion control rate, stable property, good compatibility, low production cost, simple process, universal applicability and the like, and has few reports in China.
Description
Technical Field
The invention relates to the technical field of oil-gas-water treatment, in particular to a multi-quaternary ammonium salt corrosion inhibitor and a preparation method thereof.
Background
The equipment corrosion and the Sulfate Reducing Bacteria (SRB) breeding are hidden dangers which seriously threaten the safety production of offshore oil fields, and some seasThe local pitting rate of the mixed water injection flow of the oil field is up to 200mpy, and H caused by SRB bacteria of the offshore oil field 2 The S concentration is up to 1000mg/L once. The breeding of SRB bacteria can also cause microbial corrosion, aggravate equipment corrosion, lead corrosion products, thalli and metabolites thereof to block stratums and pipelines, reduce stratum permeability, damage oil layers, increase the pressure of a water injection system, cause the reduction of water injection quantity, petroleum yield and oil gas quality, are extremely unfavorable for offshore oil field development and bring serious difficulty for subsequent crude oil processing.
The method for preventing equipment corrosion in the offshore oilfield comprises the following steps: wrapping an anticorrosive coating, implementing cathodic protection, replacing an anticorrosive material, adding a corrosion inhibitor and the like.
At present, adding the corrosion inhibitor is still one of the most convenient and effective methods for preventing corrosion damage.
The surface activity of the dumpling salt is strong, and the dumpling salt has good functions of adsorption, chelation, synergy and the like, so the dumpling salt is widely applied as a corrosion inhibitor. Due to unique structural advantages, the multi-quaternary ammonium salt has more excellent performance than the traditional single-chain single-cation single-quaternary ammonium salt, which is hereinafter referred to as single-quaternary double salt). The dumpling salt molecule contains a plurality of cationic head groups and long-chain hydrophobic groups, and the middle of the dumpling salt molecule is formed by connecting a connecting group. Each cationic head group may be composed of a group containing a lone pair of electrons, a group containing a heteroatom such as N, O, S, P, a heterocyclic quaternary nitrogen atom, a quaternary nitrogen atom with a long alkyl chain, a reactive group such as a hydroxyl group, and the linking group may be a short chain (2 atoms) or a long chain (more than 20 atoms), a rigid chain (e.g., stilbene) or a flexible chain (e.g., multiple ethylene glycol groups), a polar chain (e.g., casein), or a non-polar chain (e.g., aliphatic and aromatic), and the like. Due to the special structures, the multi-season dumpling salt has higher surface activity than the traditional single-season salt and biquaternary ammonium salt, is easier to adsorb the surface of the thousand metals, improves the corrosion inhibition performance, and has other unique performances such as high resistance, solubility enhancement, rheological property, good calcium soap dispersing capacity, temperature resistance, good synergistic effect capability and the like.
Disclosure of Invention
The invention overcomes the defects in the prior art, and the produced liquid of the existing oil well contains a large amount of water and has mineralization degreeHigh, crude oil associated gas containing CO 2 、H 2 The invention provides a multi-quaternary ammonium salt corrosion inhibitor and a preparation method thereof, wherein the corrosion problem frequently occurs due to various conditions of breeding and propagation of corrosive bacteria SRB and the like, and the multi-quaternary ammonium salt corrosion inhibitor has the characteristics of strong adsorption capacity, quick film formation, low corrosion rate control, stable property, good compatibility, low production cost, simple process, universal applicability and the like.
The purpose of the invention is realized by the following technical scheme.
A multi-quaternary ammonium salt corrosion inhibitor and a preparation method thereof are carried out according to the following steps:
step 1, uniformly mixing polyamine and epoxy chloropropane, placing at 0-40 ℃, reacting for 10-18h to obtain a polychlorinated substituent A, wherein the mass ratio of the polyamine to the epoxy chloropropane is 1:1-1:12;
and 2, uniformly mixing the polychlorinated substituent A prepared in the step 1 with a nitrogen-containing compound, placing the mixture at 90-150 ℃, and stirring the mixture for reaction for 5-8 hours to obtain a polyquaternary ammonium salt B, wherein the mass ratio of the polychlorinated substituent A to the nitrogen-containing compound is 1:1-1:12;
and 3, mixing the polyquaternary ammonium salt B prepared in the step 2 with ethanol, thiourea and acetic acid, and uniformly stirring to obtain the polyquaternary ammonium salt corrosion inhibitor, wherein the mass ratio of the polyquaternary ammonium salt B to the ethanol to the thiourea to the acetic acid is (5-8): (2-4): (1-2): (1-2).
In the step 1, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethylene polyamine is adopted as the polyamine, and the ratio of the polyamine to the epichlorohydrin is 1:1-1:10.
in the step 1, the reaction temperature of polyamine and epichlorohydrin is 0-35 ℃, and the reaction time is 12-16h.
In the step 2, the nitrogen-containing compound adopts oleic acid diethylenetriamine imidazoline or pyridine or dodecyl dimethyl tertiary amine, and the mass ratio of the polychlorinated substituent A to the nitrogen-containing compound is 1:1-1:10.
in the step 2, the reaction temperature of the polychlorinated substituent A and the nitrogen-containing compound is 100-130 ℃, and the stirring reaction time is 6 hours.
The invention has the beneficial effects that: the multi-quaternary ammonium salt corrosion inhibitor obtained by the invention is characterized in that groups containing lone pair electrons, groups containing hetero atoms such as N, O, S, P, heterocyclic quaternary nitrogen atoms and quaternary nitrogen atoms with long alkyl chains are mainly introduced, and coordination bonds are formed by the lone pair electrons of the nitrogen atoms and empty orbitals of iron elements, so that the contact between water quality and metal pipeline materials is isolated, and a good corrosion inhibition effect is achieved.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
(1) Mixing 10.3g of diethylenetriamine and 46g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 1:5), reacting at the normal temperature of below 35 ℃, and stirring for 16 hours to obtain a polychlorinated substituent A1;
(2) Uniformly mixing the polychlorinated substituent A1 obtained in the step (1) with 175g of oleic acid diethylenetriamine imidazoline (industrial grade, with the mass concentration of 99%) (wherein the mass ratio of the polychlorinated substituent A1 to the oleic acid diethylenetriamine imidazoline is 1:5), heating to 110 ℃, and stirring for 6 hours to obtain a quaternary ammonium salt B1 through reaction;
(3) Mixing the organic amine ester B1 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 2
(1) Mixing 10.3g of diethylenetriamine and 46g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 1:5), reacting at the normal temperature of below 30 ℃, and stirring for 14h to obtain a polychlorinated substituent A2;
(2) Uniformly mixing the polychlorinated substituent A2 obtained in the step (1) with 39.5g of pyridine (industrial grade, the mass concentration is 99%) (wherein the mass ratio of the polychlorinated substituent A2 to the pyridine is 1:5), heating to 110 ℃, and stirring for 6 hours to obtain quaternary ammonium salt B2;
(3) Mixing the organic amine ester B2 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 3
(1) Mixing 10.3g of diethylenetriamine and 46g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 1:5), reacting at the normal temperature of below 30 ℃, and stirring for 12 hours to obtain a polychlorinated substituent A3;
(2) Uniformly mixing the polychlorinated substituent A3 obtained in the step (1) with 106.5g of dodecyl dimethyl tertiary amine (industrial grade, mass concentration is 97%) (wherein the mass ratio of the polychlorinated substituent A3 to the dodecyl dimethyl tertiary amine is 1:5), heating to 110 ℃, and stirring for 6 hours to obtain quaternary ammonium salt B3;
(3) Mixing the organic amine ester B3 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 4
(1) Mixing 14.6g of triethylene tetramine and 55.5g of epichlorohydrin (wherein the mass ratio of the triethylene tetramine to the epichlorohydrin is 1:6), reacting at the normal temperature of below 35 ℃, and stirring for 16 hours to obtain a polychlorinated substituent A4;
(2) Uniformly mixing the polychlorinated substituent A4 obtained in the step (1) with 210g of oleic acid diethylenetriamine imidazoline (industrial grade, with the mass concentration of 99%) (wherein the mass ratio of the polychlorinated substituent A4 to the oleic acid diethylenetriamine imidazoline is 1:6), heating to 120 ℃, stirring for 6 hours, and reacting to obtain quaternary ammonium salt B4;
(3) Mixing the organic amine ester B4 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, stirring uniformly to obtain the corrosion inhibitor.
Example 5
(1) Mixing 14.6g of triethylene tetramine and 55.5g of epichlorohydrin (wherein the mass ratio of the triethylene tetramine to the epichlorohydrin is 1:6), reacting at the normal temperature of below 30 ℃, and stirring for 14 hours to obtain a polychlorinated substituent A5;
(2) Uniformly mixing the polychlorinated substituent A5 obtained in the step (1) with 47.4g of pyridine (industrial grade, the mass concentration is 99%) (wherein the mass ratio of the polychlorinated substituent A5 to the pyridine is 1:6), heating to 120 ℃, stirring for 6h, and reacting to obtain quaternary ammonium salt B5;
(3) Mixing the organic amine ester B5 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 6
(1) Mixing 14.6g of triethylene tetramine and 55.5g of epichlorohydrin (wherein the mass ratio of the triethylene tetramine to the epichlorohydrin is 1:6), reacting at the normal temperature of below 30 ℃, and stirring for 12 hours to obtain a polychlorinated substituent A6;
(2) Uniformly mixing the A6 obtained in the step (1) with 128.04g dodecyl dimethyl tertiary amine (industrial grade, mass concentration is 97%) (wherein the mass ratio of the polychlorinated substituent A6 to the dodecyl dimethyl tertiary amine is 1:6), heating to 120 ℃, and stirring for 6 hours to obtain quaternary ammonium salt B6;
(3) Mixing the organic amine ester B6 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio of the organic amine ester B6 to the acetic acid is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 7
(1) Firstly, 18.9g of tetraethylenepentamine and 64.4g of epoxy chloropropane are mixed (wherein the mass ratio of the tetraethylenepentamine to the epoxy chloropropane is 1:7), and the mixture is reacted at the normal temperature of below 35 ℃ and stirred for 16 hours to obtain a polychlorinated substituent A7;
(2) Uniformly mixing the polychlorinated substituent A7 obtained in the step (1) with 245g of oleic acid diethylenetriamine imidazoline (industrial grade, with the mass concentration of 99%) (wherein the mass ratio of the polychlorinated substituent A7 to the oleic acid diethylenetriamine imidazoline is 1:7), heating to 130 ℃, stirring for 6 hours, and reacting to obtain quaternary ammonium salt B7;
(3) Mixing the organic amine ester B7 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 8
(1) Firstly, 18.9g of tetraethylenepentamine and 64.4g of epoxy chloropropane are mixed (wherein the mass ratio of the tetraethylenepentamine to the epoxy chloropropane is 1:7), and the mixture is reacted at the normal temperature of below 30 ℃ and stirred for 14h to obtain a polychlorinated substituent A8;
(2) Uniformly mixing the polychlorinated substituent A8 obtained in the step (1) with 55.4g of pyridine (industrial grade, the mass concentration is 99%) (wherein the mass ratio of the polychlorinated substituent A8 to the pyridine is 1:7), heating to 120 ℃, stirring for 6h, and reacting to obtain quaternary ammonium salt B8;
(3) Mixing the organic amine ester B8 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 9
(1) Firstly, 18.9g of tetraethylenepentamine and 64.4g of epoxy chloropropane are mixed (wherein the mass ratio of the tetraethylenepentamine to the epoxy chloropropane is 1:7), and the mixture is reacted at the normal temperature of below 30 ℃ and stirred for 12 hours to obtain a polychlorinated substituent A9;
(2) Uniformly mixing the A9 obtained in the step (1) with 149.1g of dodecyl dimethyl tertiary amine (industrial grade, mass concentration is 97%) (wherein the mass ratio of the polychlorinated substituent A9 to the dodecyl dimethyl tertiary amine is 1:7), heating to 100 ℃, stirring for 6h, and reacting to obtain quaternary ammonium salt B9;
(3) Mixing the organic amine ester B9 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 10
(1) Mixing 20g of polyethylene polyamine and 92g of epoxy chloropropane (wherein the mass ratio of tetraethylenepentamine to epoxy chloropropane is 1;
(2) Uniformly mixing the polychlorinated substituent A10 obtained in the step (1) with 350g of oleic acid diethylenetriamine imidazoline (industrial grade, with the mass concentration of 99%) (wherein the mass ratio of the polychlorinated substituent A10 to the oleic acid diethylenetriamine imidazoline is 1);
(3) Mixing the organic amine ester B10 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 11
(1) Firstly, mixing 20g of polyethylene polyamine and 92g of epoxy chloropropane (wherein the mass ratio of tetraethylenepentamine to the epoxy chloropropane is 1);
(2) Uniformly mixing the polychlorinated substituent A11 obtained in the step (1) with 79.1g of pyridine (industrial grade, the mass concentration is 99%) (wherein the mass ratio of the polychlorinated substituent A8 to the pyridine is 1) and heating to 120 ℃, stirring for 6h, and reacting to obtain quaternary ammonium salt B11;
(3) Mixing the organic amine ester B11 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
Example 12
(1) Mixing 20g of polyethylene polyamine and 92g of epoxy chloropropane (wherein the mass ratio of tetraethylenepentamine to the epoxy chloropropane is 1);
(2) Uniformly mixing the A12 obtained in the step (1) with 213.4g of dodecyl dimethyl tertiary amine (industrial grade, mass concentration is 97%) (wherein the mass ratio of the polychlorinated substituent A12 to the dodecyl dimethyl tertiary amine is 1: 10), heating to 100 ℃, stirring for 6h, and reacting to obtain quaternary ammonium salt B12;
(3) Mixing the organic amine ester B12 obtained in the step (2) with ethanol, thiourea and acetic acid, wherein the mass ratio is 6:3:3:1, uniformly stirring to obtain the multi-quaternary ammonium salt corrosion inhibitor.
The first test example:
experiment raw materials: certain offshore oilfield FPSO produced water (degree of mineralization 30000 mg/L)
Experiment temperature: 70 deg.C
The concentration of the medicament: 10mg/L
Evaluation criteria: SY/T5273 evaluation method for corrosion inhibitor performance of oilfield produced water
The evaluation method comprises the following steps: soaking the steel test piece in absolute ethyl alcohol for about 5 minutes, taking out the test piece, wiping the test piece by using filter paper, drying the test piece wrapped by using cold air, drying the test piece in a dryer for 30 minutes, and weighing the test piece (the weight is accurate to 0.0001 g).
Pouring 2.2L of experimental water sample into an autoclave, adding a corrosion inhibitor, fixing a steel test piece in a polytetrafluoroethylene groove of an autoclave hanging piece system, filling the autoclave, sequentially introducing nitrogen, vacuumizing to remove oxygen in the autoclave, and adding a corrosion inhibitor into the autoclaveInternal injection of CO at a pressure of 0.2MPa 2 And the total supplementary pressure is increased to 1.3MPa by nitrogen, the rotation speed is set to 450rpm at the temperature of 70 ℃, and the film is dynamically hung for 3 days to obtain corrosion test data under the condition of carbon dioxide, wherein the data are shown in table 1.
TABLE 1 Corrosion test data under carbon dioxide conditions
Experiment raw materials: certain offshore oilfield FPSO produced water (degree of mineralization 30000 mg/L)
Experiment temperature: 70 deg.C
The concentration of the medicament: 10mg/L
Evaluation criteria: SY/T5273 evaluation method for corrosion inhibitor performance of oilfield produced water
The evaluation method comprises the following steps: soaking the steel test piece in absolute ethyl alcohol for about 5 minutes, taking out the test piece, wiping the test piece by using filter paper, drying the test piece wrapped by using cold air, drying the test piece in a dryer for 30 minutes, and weighing the test piece (the weight is accurate to 0.0001 g).
Pouring 2.2L of experimental water sample into an autoclave, adding a corrosion inhibitor, fixing a steel test piece in a polytetrafluoroethylene groove of an autoclave hanging piece system, filling the autoclave, sequentially introducing nitrogen and vacuumizing to remove oxygen in the autoclave, and injecting CO with the pressure of 0.2MPa into the autoclave 2 And 500mg/L of H 2 And S, using nitrogen to make up the total pressure to 1.3MPa, controlling the temperature at 70 ℃, setting the rotating speed at 450rpm, dynamically hanging the film for 3 days, and obtaining the corrosion test data under the conditions of carbon dioxide and hydrogen sulfide, as shown in Table 2.
TABLE 2 Corrosion test data under carbon dioxide and hydrogen sulfide conditions
Test example two:
experiment raw materials: 9% (mass fraction) formic acid: 6% (mass fraction) acetic acid aqueous solution =1:1 (mass ratio)
Experiment temperature: 90 deg.C
The concentration of the medicament: 1% (mass fraction)
Evaluation criteria: SY/T5273 evaluation method for corrosion inhibitor performance of oilfield produced water
SY-T5405-1996 corrosion inhibitor performance test method and evaluation index for acidification
The evaluation method comprises the following steps: soaking the steel test piece in absolute ethyl alcohol for about 5 minutes, taking out the test piece, wiping the test piece by using filter paper, drying the test piece wrapped by using cold air, drying the test piece in a drier for 30 minutes, and weighing (the accuracy is 0.0001 g).
The method is carried out under the condition that the water body is not deoxidized and dissolved oxygen is directly reserved, a corrosion inhibitor sample with the mass concentration of 1% is added into 100mL of water sample, a 20# steel metal hanging piece is hung, standing is carried out for 4 hours, and corrosion test data under the organic acid condition are obtained, and are shown in table 3.
TABLE 3 Corrosion test data under organic acid conditions
According to the test examples, the multi-quaternary ammonium salt corrosion inhibitor has the characteristics of small dosage and high corrosion inhibition rate in a system for producing water and organic acid from a water source of an offshore oilfield.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. A multi-quaternary ammonium salt corrosion inhibitor is characterized in that: the method comprises the following steps:
step 1, uniformly mixing polyamine and epoxy chloropropane, placing at 0-40 ℃, reacting for 10-18h to obtain a polychlorinated substituent A, wherein the mass ratio of the polyamine to the epoxy chloropropane is (1:1) — (1; the polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or polyethylene polyamine;
step 2, uniformly mixing the polychlorinated substituent A prepared in the step 1 with a nitrogen-containing compound, placing the mixture at 90-150 ℃, and stirring the mixture for reaction for 5-8 hours to obtain a polyquaternary ammonium salt B, wherein the mass ratio of the polychlorinated substituent A to the nitrogen-containing compound is (1:1) — (1; the nitrogen-containing compound adopts oleic acid diethylenetriamine imidazoline or pyridine or dodecyl dimethyl tertiary amine;
and 3, mixing the polyquaternary ammonium salt B prepared in the step 2 with ethanol, thiourea and acetic acid, and uniformly stirring to obtain the polyquaternary ammonium salt corrosion inhibitor, wherein the mass ratio of the polyquaternary ammonium salt B to the ethanol to the thiourea to the acetic acid is (5-8): (2-4): (1-2): (1-2).
2. The multi-quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that: in the step 1, the reaction temperature of polyamine and epichlorohydrin is 0-35 ℃, and the reaction time is 12-16h.
3. The multi-quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that: in the step 2, the reaction temperature of the polychlorinated substituent A and the nitrogen-containing compound is 100-130 ℃, and the stirring reaction time is 6 hours.
4. A preparation method of a multi-quaternary ammonium salt corrosion inhibitor is characterized by comprising the following steps: the method comprises the following steps:
step 1, uniformly mixing polyamine and epoxy chloropropane, placing at 0-40 ℃, reacting for 10-18h to obtain a polychlorinated substituent A, wherein the mass ratio of the polyamine to the epoxy chloropropane is (1:1) — (1; the polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or polyethylene polyamine;
step 2, uniformly mixing the polychlorinated substituent A prepared in the step 1 with a nitrogen-containing compound, placing the mixture at 90-150 ℃, and stirring the mixture for reaction for 5-8 hours to obtain a polyquaternary ammonium salt B, wherein the mass ratio of the polychlorinated substituent A to the nitrogen-containing compound is (1:1) — (1; the nitrogen-containing compound adopts oleic acid diethylenetriamine imidazoline or pyridine or dodecyl dimethyl tertiary amine;
and 3, mixing the polyquaternary ammonium salt B prepared in the step 2 with ethanol, thiourea and acetic acid, and uniformly stirring to obtain the polyquaternary ammonium salt corrosion inhibitor, wherein the mass ratio of the polyquaternary ammonium salt B to the ethanol to the thiourea to the acetic acid is (5-8): (2-4): (1-2): (1-2).
5. The method for preparing the polyquaternium corrosion inhibitor according to claim 4, wherein in the step 1, the reaction temperature of the polyamine and the epichlorohydrin is 0-35 ℃, and the reaction time is 12-16h.
6. The method for preparing the multi-quaternary ammonium salt corrosion inhibitor according to claim 4, wherein in the step 2, the reaction temperature of the polychlorinated substituent A and the nitrogen-containing compound is 100-130 ℃, and the stirring reaction time is 6 hours.
7. The use of a polyquaternium corrosion inhibitor as claimed in any of claims 1 to 3 in the corrosion protection of offshore oilfield equipment, wherein: the corrosion inhibition rate of the multi-quaternary ammonium salt corrosion inhibitor is 82.80-92.50% under the condition of carbon dioxide, the corrosion inhibition rate of the multi-quaternary ammonium salt corrosion inhibitor is 87.90-91.90% under the condition of carbon dioxide and hydrogen sulfide, and the corrosion inhibition rate of the multi-quaternary ammonium salt corrosion inhibitor is 99.20-99.50% under the condition of organic acid, wherein the organic acid is a mixed aqueous solution of 9% formic acid and 6% acetic acid in mass fraction.
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