CN107418548A - A kind of pyridine derivate and Mannich base combined high temperature acidification corrosion inhibitor - Google Patents
A kind of pyridine derivate and Mannich base combined high temperature acidification corrosion inhibitor Download PDFInfo
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- CN107418548A CN107418548A CN201710756053.XA CN201710756053A CN107418548A CN 107418548 A CN107418548 A CN 107418548A CN 201710756053 A CN201710756053 A CN 201710756053A CN 107418548 A CN107418548 A CN 107418548A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 102
- 238000005260 corrosion Methods 0.000 title claims abstract description 102
- 239000003112 inhibitor Substances 0.000 title claims abstract description 78
- 230000020477 pH reduction Effects 0.000 title claims abstract description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract 3
- -1 dimethylamino methyl phenylpropyl Chemical group 0.000 claims abstract description 26
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000003222 pyridines Chemical class 0.000 claims description 21
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 8
- DCZPFJUDGYHRRB-UHFFFAOYSA-N CC1=NNN=C1CCC(C2=CC=CC=C2)N(C)C Chemical compound CC1=NNN=C1CCC(C2=CC=CC=C2)N(C)C DCZPFJUDGYHRRB-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- GAOYBSJOKJLORU-UHFFFAOYSA-N N,N,4-trimethyl-2H-benzotriazol-5-amine Chemical compound CN(C)C1=C(C2=C(NN=N2)C=C1)C GAOYBSJOKJLORU-UHFFFAOYSA-N 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 15
- 238000010276 construction Methods 0.000 abstract description 14
- 239000000654 additive Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- QIMIIPRYMYRYFC-RPPGKUMJSA-N 4-[(e)-(4-chlorophenyl)methylideneamino]-5-(2,4-dichloro-5-fluorophenyl)-2-[(4-methylpiperazin-1-yl)methyl]-1,2,4-triazole-3-thione Chemical compound C1CN(C)CCN1CN1C(=S)N(\N=C\C=2C=CC(Cl)=CC=2)C(C=2C(=CC(Cl)=C(F)C=2)Cl)=N1 QIMIIPRYMYRYFC-RPPGKUMJSA-N 0.000 abstract 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract 1
- 229960004011 methenamine Drugs 0.000 abstract 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract 1
- DRTZAIDVOGUYSP-UHFFFAOYSA-N pyridin-1-ium;chloride;hydrochloride Chemical compound Cl.Cl.C1=CC=NC=C1 DRTZAIDVOGUYSP-UHFFFAOYSA-N 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 239000003129 oil well Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011435 rock Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ALDULCLMMQLMIO-UHFFFAOYSA-N 1-(2h-benzotriazol-4-yl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=CC2=C1N=NN2 ALDULCLMMQLMIO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
- C07D253/10—Condensed 1,2,4-triazines; Hydrogenated condensed 1,2,4-triazines
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- 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
- 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
- C09K2208/32—Anticorrosion additives
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of pyridine derivate and Mannich base combined high temperature acidification corrosion inhibitor, the hydroxy propane of 1,3 dichloride pyridine 2 of dimethylamino methyl phenylpropyl alcohol triazole Mannich base and 10~20 parts by weight, the methenamine of 3~5 parts by weight, the synergist of 5~7 parts by weight, the surfactant of 0.5~1 parts by weight, the dispersant of 2~3 parts by weight, the solvent of 40~60 parts by weight, the triethanolamine of 3~5 parts by weight and the formic acid of 5.0~9.0 parts by weight including 10~18 parts by weight；A kind of pyridine derivate and Mannich base combined high temperature acidification corrosion inhibitor is applied to 120~160 DEG C, have the compound slow corrosion agent prescription of excellent " property is stable, corrosion inhibition is good, is easy to site operation and cost advantage " concurrently simultaneously, the system is good with the imidazoline inhibitor good, conventional with the conventional acidizing additive compatibility in scene, other kinds of quaternary ammonium salt corrosion inhibitor compatibility, can be used in mixed way, easy for construction and high safety, convenience in transport store the features such as low with cost.
Description
Technical Field
The invention relates to the technical field of oilfield acidification construction, in particular to a pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor.
Background
In the acidification of oil and gas wells, particularly in the acidification of concentrated hydrochloric acid or a large amount of acid in high-temperature deep wells and ultra-deep wells, the first task is to solve the problem of corrosion of high-temperature acidification liquid to oil well casing equipment. In the pickling process, particularly the pickling solution prepared by inorganic acid causes a certain degree of corrosion and damage to metal equipment and materials. In addition, hydrogen generated after the reaction of the metal and the acid causes hydrogen embrittlement corrosion to metal equipment, and a large amount of acid gas is brought out to form acid mist, so that the working conditions of the downhole operation tool and the downhole pipe column are further deteriorated under the high-temperature condition, and therefore, a targeted corrosion inhibition measure must be taken on the metal corrosion under the high-temperature environment. The high-temperature acidizing corrosion inhibitor is mainly used for preventing hydrochloric acid or earth acid solution from corroding metal equipment or an underground pipe column during acidizing construction of a high-temperature oil well so as to ensure implementation of an acidizing and fracturing process of the oil well and realization of technical measures for increasing and stabilizing yield. In the past, when a concentrated hydrochloric acid is adopted to acidify an oil well in an oil field at a high temperature, accidents such as tripping of an underground oil pipe and the like often occur due to the fact that a good corrosion inhibitor is not used for corrosion prevention. Therefore, in the process of acidizing construction of a high-temperature high-pressure oil well, the high-temperature acidizing corrosion inhibitor is added into the acid liquor to inhibit the corrosion of the acid liquor to the underground pipe column.
With the development of the drilling process and the improvement of the oil extraction technology, a large number of deep wells and ultra-deep wells are put into development, the amount of acidification measures is increased year by year, and higher requirements on the performance of the corrosion inhibitor for acidification are provided. The acidizing corrosion inhibitor performance is greatly reduced when the well temperature exceeds 120 ℃, although the purpose of corrosion inhibition can be realized by a well washing and temperature reduction mode before acidizing, the corrosion inhibition can not be realized if a pump is stopped abnormally midway or a well without well washing conditions is generated in the acidizing process. According to the field use condition, the high-temperature acidizing corrosion inhibitor commonly used in China at present has the following problems at high temperature:
(1) under the environment of high temperature and high pressure, the single component or single agent can hardly achieve ideal effect, different corrosion inhibitors are compounded to exert the synergistic effect, and the composite acidizing corrosion inhibitor with better performance, economy and practicability is developed to achieve the purposes of high performance and multiple functions;
(2) in recent years, although there have been many researches on oil well acidizing corrosion inhibitors, there are few varieties of acidizing corrosion inhibitors suitable for high temperature, and the performances are not stable enough. The defects of easy coking, delamination, poor solubility and dispersibility and insufficient stability of part of high-temperature acidizing corrosion inhibitors at high temperature can cause further damage to the stratum. Therefore, the development of the oil well acidizing corrosion inhibitor with high temperature resistance and good effect is an urgent need of acidizing and production increasing measures for oil and gas fields, and has important significance for improving the acidizing effect, reducing the corrosion of equipment and pipelines and increasing comprehensive economic benefits. The composite corrosion inhibitor can improve the adsorption coverage and the adsorption stability by utilizing the synergistic effect among the corrosion inhibitors, change the adsorption speed, reduce the consumption of the corrosion inhibitors, reduce the toxicity of the corrosion inhibitors, prepare the composite corrosion inhibitor with higher corrosion inhibition efficiency, expand the demand range of the corrosion inhibitor and solve the difficulty that single components are difficult to overcome.
Disclosure of Invention
The invention aims to provide a pyridine derivative and Mannich base composite high-temperature acidizing corrosion inhibitor which is stable in property, good in corrosion inhibition performance and capable of meeting requirements of oil field acidizing construction under the condition of 120-160 ℃.
Therefore, the technical scheme of the invention is as follows:
a pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises 10-18 parts by weight of dimethylamino methyl phenylpropyl triazole Mannich base, 10-20 parts by weight of 1, 3-dichloropyridine-2-hydroxypropane, 3-5 parts by weight of urotropine, 5-7 parts by weight of a synergist, 0.5-1 part by weight of a surfactant, 2-3 parts by weight of a dispersant, 40-60 parts by weight of a solvent, 3-5 parts by weight of triethanolamine and 5.0-9.0 parts by weight of formic acid.
The structural formula of the dimethylamino methyl phenylpropyl triazole Mannich base is shown as the following formula I:
the preparation method comprises the following steps: adding benzotriazole, benzaldehyde and dimethylamine in a molar ratio of 3:2:3 into a reaction bottle, and uniformly mixing; dropwise adding hydrochloric acid to adjust the pH value of the mixed solution to 4, heating to 90 ℃, reacting for 4 hours, and distilling to obtain a crude product; mixing the obtained crude product and absolute ethyl alcohol according to the proportion of 1: adding 4 volumes of the precipitate into a beaker to obtain a white precipitate product, standing for precipitation, removing a layer solution, continuously washing and filtering the white precipitate product with absolute ethyl alcohol for 2-3 times, and finally vacuum-drying the obtained precipitate product for 5 hours for later use.
The structural formula of the 1, 3-dichloropyridine-2-hydroxypropane is shown as the following formula II:
the preparation method comprises the following steps: adding 20 wt.% of HCl and quinoline with the molar ratio of 1: 2-2.1 into a three-neck flask provided with a reflux condenser, a thermometer, an electric heating jacket and a stirring device, stirring and reacting at 60 ℃ for 1h, then sequentially dropwise adding epoxy chloropropane and quinoline into the reaction liquid, wherein the molar ratio of epoxy chloropropane to quinoline is 1: 1-1.1, continuing to react for 4h, and cooling to room temperature to obtain a crude product; extracting the crude product with petroleum ether, and removing petroleum ether solvent and insoluble substances in the solution by reduced pressure distillation to obtain reddish brown liquid, namely 1, 3-dichloropyridine-2-hydroxypropane.
The synergist is a mixture of propiolic alcohol and potassium iodide, and the weight ratio of the propiolic alcohol to the potassium iodide is 3-7: 1-2.
The surfactant is linear alkyl benzene sodium sulfonate.
The solvent is a mixed solution of methanol and polypropylene glycol-400 (PPG-400 for short), and the weight ratio of the methanol to the polypropylene glycol-400 is 2-5: 1-2.
The dispersing agent is a mixture of OP-10 and peregal O, and the weight ratio of the OP-10 to the peregal O is 1-2: 1-1.5; wherein the structural formula of the peregal O is as follows: RO- (CH)2CH2O)n-H，R＝C16～C18And n is 9-30, and specifically, any one of O-9, O-10, O-15, O-20, O-25, O-30 and O-35 can be mixed with OP-10 in a certain proportion to be used as a dispersing agent.
The key point of the invention is that the Mannich base of dimethylamino methyl phenyl triazole and 1, 3-dichloropyridine-2-hydroxypropane are compounded, and a certain proportion of synergist, dispersant, solvent and surfactant are compounded at the same time, so that the acidizing corrosion inhibitor has more stable property under the acidizing condition of 120-160 ℃ after the compounding treatment.
The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor can realize slow release performance when the addition amount of the pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor in an acid liquor system is 2.0-4.0 wt.%.
The pyridine derivative and Mannich base composite high-temperature acidizing corrosion inhibitor has the beneficial effects that:
(1) in 0-20% (mass fraction, the same below) of HCl and earth acid system (12% HCl and 3% HF, volume fraction), the corrosion inhibition rate of N80 steel sheet at 120-160 ℃ meets the requirement of the first-grade corrosion inhibitor product index in the oil industry standard SY/T5405-1996;
(2) the corrosion inhibition performance of the composite high-temperature acidification corrosion inhibitor is maintained for more than 3 days at 160 ℃, or the corrosion inhibition performance can be stably exerted for a longer time, so that the acidification construction quality at 160 ℃ is improved;
(3) the composite high-temperature acidizing corrosion inhibitor is easy to store and transport, the composite corrosion inhibitor is not decayed in the long-time storage and transport process, the centrally prepared composite corrosion inhibitor is convenient to distribute to a plurality of wells for acidizing construction measure transformation, the on-site use is easy, and only 2.0-4.0 wt.% of the composite corrosion inhibitor is required to be added into a required acid liquor system;
(4) the composite high-temperature acidizing corrosion inhibitor has better compatibility with a common oil field acidizing system, is convenient to compound with different acidizing systems, and has wide application range;
(5) the composite high-temperature acidizing corrosion inhibitor has stable property, is non-combustible when meeting open fire, and has high construction safety;
(6) the composite high-temperature acidizing corrosion inhibitor has no biotoxicity, can be biodegraded in a natural environment, and meets the requirements of acidizing the marine petroleum;
(7) the preparation method of the composite high-temperature acidizing corrosion inhibitor is simple, the raw materials are easy to obtain, and the composite high-temperature acidizing corrosion inhibitor is suitable for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the invention in any way.
Example 1
A pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises 15 parts by weight of dimethylamino methyl phenylpropyl triazole Mannich base, 10 parts by weight of 1, 3-dichloropyridine-2-hydroxypropane, 3.0 parts by weight of urotropine, 3.0 parts by weight of propiolic alcohol, 1.0 part by weight of potassium iodide, 0.5 part by weight of LAS, 1.0 part by weight of peregal O, 1.5 parts by weight of OP-10, 40 parts by weight of methanol, 15 parts by weight of PPG-400, 5.0 parts by weight of triethanolamine and 5.0 parts by weight of formic acid.
When in use, the components are weighed, mixed evenly and then sent to a construction site for use or stored for standby.
Example 2
A pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises 18 parts by weight of dimethylamino methyl phenylpropyl triazole Mannich base, 12 parts by weight of 1, 3-dichloropyridine-2-hydroxypropane, 5.0 parts by weight of urotropine, 4.0 parts by weight of propiolic alcohol, 1.0 part by weight of potassium iodide, 1.0 part by weight of LAS, 2.0 parts by weight of peregal O, 1.0 part by weight of OP-10, 31 parts by weight of methanol, 15 parts by weight of PPG-400, 5.0 parts by weight of triethanolamine and 5.0 parts by weight of formic acid.
When in use, the components are weighed, mixed evenly and then sent to a construction site for use or stored for standby.
Example 3
A pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises 15 parts by weight of dimethylamino methyl phenylpropyl triazole Mannich base, 15 parts by weight of 1, 3-dichloropyridine-2-hydroxypropane, 5.0 parts by weight of urotropine, 3.0 parts by weight of propiolic alcohol, 2.0 parts by weight of potassium iodide, 0.5 part by weight of LAS, 1.5 parts by weight of peregal O, 1.0 part by weight of OP-10, 31 parts by weight of methanol, 15 parts by weight of PPG-400, 5.0 parts by weight of triethanolamine and 5.0 parts by weight of formic acid.
When in use, the components are weighed, mixed evenly and then sent to a construction site for use or stored for standby.
Example 4
A pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises, by weight, 17 parts of dimethylamino methyl phenylpropyl triazole Mannich base, 17 parts of 1, 3-dichloropyridine-2-hydroxypropane, 5.0 parts of urotropine, 3.0 parts of propiolic alcohol, 2.0 parts of potassium iodide, 1.0 part of LAS, 1.0 part of peregal O, 1.0 part of OP-10, 26 parts of methanol, 15 parts of PPG-400, 3.0 parts of triethanolamine and 9.0 parts of formic acid.
When in use, the components are weighed, mixed evenly and then sent to a construction site for use or stored for standby.
Example 5
A pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor comprises, by weight, 10 parts of dimethylamino methyl phenyl triazole Mannich base, 20 parts of 1, 3-dichloropyridine-2-hydroxypropane, 3.0 parts of urotropine, 5.0 parts of propiolic alcohol, 2.0 parts of potassium iodide, 0.5 part of LAS, 1.5 parts of peregal O, 1.0 part of OP-10, 29 parts of methanol, 20 parts of PPG-400, 3.0 parts of triethanolamine and 5.0 parts of formic acid.
When in use, the components are weighed, mixed evenly and then sent to a construction site for use or stored for standby.
Except for the dimethylaminomethylbenzotriazole Mannich base and the 1, 3-dichloropyridine-2-hydroxypropane, the rest components in the embodiments 1 to 5 and the raw materials for preparing the dimethylaminomethylbenzotriazole Mannich base and the 1, 3-dichloropyridine-2-hydroxypropane are purchased from commercial products.
Specifically, the preparation method of the dimethylamino methyl phenyl triazole Mannich base comprises the following steps: adding benzotriazole, benzaldehyde and dimethylamine in a molar ratio of 3:2:3 into a reaction bottle, and uniformly mixing; dropwise adding hydrochloric acid to adjust the pH value of the mixed solution to 4, heating to 90 ℃, reacting for 4 hours, distilling, and collecting fractions except the temperature interval of reactants and the solvent to obtain a crude product; mixing the obtained crude product and absolute ethyl alcohol according to the proportion of 1: adding 4 volumes of the precipitate into a beaker to obtain a white precipitate product, standing for precipitation, removing a layer solution, continuously washing and filtering the white precipitate product with absolute ethyl alcohol for 2-3 times, and finally vacuum-drying the obtained precipitate product for 5 hours for later use.
The preparation method of the 1, 3-dichloropyridine-2-hydroxypropane comprises the following steps: adding 20 wt.% of HCl and quinoline with the molar ratio of 1:2.1 into a reaction bottle, stirring and reacting at 60 ℃ for 1h, then sequentially dropwise adding epoxy chloropropane and quinoline into the reaction solution, wherein the molar ratio of epoxy chloropropane to quinoline is 1:1.1, continuing to react for 4h, and then cooling to room temperature; extracting the product with petroleum ether, separating and standing, taking the upper layer of reddish brown liquid, and removing insoluble substances and the petroleum ether solvent in the solution through reduced pressure distillation to finally obtain the reddish brown liquid, namely the 1, 3-dichloropyridine-2-hydroxypropane.
And (3) performance testing:
the pyridine derivative and the Mannich base composite high-temperature acidizing corrosion inhibitor prepared in the embodiments 1-5 are respectively tested from the aspects of corrosion inhibition performance, dissolution and dispersion performance, core permeability damage experiments and the like.
The corrosion inhibition performance test comprises the following steps:
and evaluating the corrosion inhibition effect at the temperature of more than 90 ℃, and evaluating according to a high-temperature high-pressure dynamic corrosion rate measuring method in the petroleum and natural gas industry standard SY/T5405-1996 (Corrosion inhibitor for acidification performance test method and evaluation index) of the people's republic of China. Pouring the prepared sample into a high-temperature high-pressure kettle, then putting the treated test piece into the kettle, starting timing when the temperature reaches the specified temperature, taking out the test piece after reacting for 4 hours for treatment, and calculating the average corrosion rate. The test results are shown in table 1 below.
Table 1:
as can be seen from Table 1 above, the addition of 2% of HCl 15 wt.%, HCl 20 wt.% and HCl 12 wt.% plus 3.0 wt.% HF at 120 ℃ can reach the first-class performance index SY/T5405-1996; under the condition of 140 ℃, the addition of 3 wt.% in 15 wt.% HCl, 20 wt.% HCl and 12 wt.% HCl +3.0 wt.% HF can reach the SY/T5405-1996 primary performance index; at 160 ℃, the addition of 4 wt.% of 15 wt.% HCl, 20 wt.% HCl and 12 wt.% HCl +3.0 wt.% HF can reach the SY/T5405-1996 primary performance index. Therefore, the corrosion inhibition rate of the composite acidizing corrosion inhibitor reaches the index requirement of a first-grade product of a petroleum industry standard SY/T5405-.
The composite acidizing corrosion inhibitors prepared in the embodiments 1 to 3 are further selected to be tested at the test temperature of 160 ℃ for corrosion rates after the corrosion inhibitors react in acid liquor with different proportions for 72 hours, and the test results are shown in the following table 2.
Table 2:
as can be seen from Table 2, the corrosion rate of steel in 15 wt.% HCl, 20 wt.% HCl, 12 wt.% HCl +3 wt.% HF at 160 ℃ increases slightly after 72h, but still can reach the first-order performance index specified in SY/T5405-1996. Therefore, the corrosion inhibitor can maintain the corrosion inhibition performance for more than 3 days at 160 ℃, or can stably exert the corrosion inhibition performance for a longer time, and effectively improve the acidification construction quality at 160 ℃.
(II) testing the dissolving and dispersing performance:
according to the corrosion inhibitor dissolution and dispersion determination method and the evaluation index in SY/T5405-1996 performance test method and evaluation index of corrosion inhibitors for acidification, the dissolution and dispersion of the corrosion inhibitors are evaluated by placing an acid liquor bottle which is uniformly mixed and contains a certain proportion of corrosion inhibitors into a constant-temperature water bath and observing the change condition of the appearance of the acid liquor.
The test results are shown in table 3 below.
Table 3:
| serial number | Time, h | Dissolution and dispersion conditions | Index (I) |
| Example one | 36 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
| Example two | 36 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
| EXAMPLE III | 36 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
| Example four | 36 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
| EXAMPLE five | 36 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
As can be seen from the test results in Table 3 above, the corrosion inhibitor has good compatibility, and no precipitation, delamination and the like appear on site within 36 hours after being mixed with common acid liquor.
And (III) testing damage of the corrosion inhibitor to the permeability of the rock core:
according to the experiment of the damage of the permeability of the rock core of the corrosion inhibitor in SY/T5405-1996 test method and evaluation index of the performance of the corrosion inhibitor for acidification, a 2.5 percent aqueous solution of the corrosion inhibitor is squeezed into the natural rock core, the permeability of the natural rock core before and after the water solution of the corrosion inhibitor is squeezed into the natural rock core is measured by a rock core flow meter, and the damage degree of the permeability of the corrosion inhibitor to the rock core is measured.
The damage rate of the corrosion inhibitor to the core permeability is calculated according to the formula (1):
in the formula: mu.si-damage to core permeability,%;
K0，Kipenetration of aqueous solution of corrosion inhibitor measured before and after kerosene injection, 10-3μm2；
i＝1，2，3，4，5。
The test results are shown in table 4 below. In table 4, the product prepared in corrosion inhibitor example 1 was used for core 1, the product prepared in corrosion inhibitor example 2 was used for core 2, and so on.
Table 4:
| serial number | K0，10-3μm2 | Ki，10-3μm2 | Permeability impairment rate,% |
| Core 1 | 9.25 | 8.87 | 4.11 |
| Core 2 | 8.13 | 7.81 | 3.94 |
| Core 3 | 11.43 | 10.82 | 5.34 |
| Core 4 | 14.23 | 13.67 | 3.94 |
| Core 5 | 10.72 | 10.01 | 6.62 |
From the above table 4, it can be seen that the permeability damage rate in the above five acid systems is below 8%, and the acid system has better reservoir protection performance and can meet the requirement of reservoir protection in actual production.
In addition, the composite corrosion inhibitor has better compatibility with common acidification systems and acidification additives (such as clay stabilizers, iron ion stabilizers, demulsification cleanup additives, precipitation inhibitors and the like) in the actual use process, and cannot generate precipitates. Is convenient to be compounded with different acidification systems, and has wide application range.
Claims (8)
1. The pyridine derivative and Mannich base composite high-temperature acidizing corrosion inhibitor is characterized by comprising 10-18 parts by weight of dimethylamino methyl benzotriazole Mannich base and 10-20 parts by weight of 1, 3-dichloropyridine-2-hydroxypropane; wherein,
the structural formula of the dimethylamino methyl phenylpropyl triazole Mannich base is shown as the following formula I:
the structural formula of the 1, 3-dichloropyridine-2-hydroxypropane is shown as the following formula II:
2. the pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 1, further comprising 3-5 parts by weight of urotropin, 5-7 parts by weight of synergist, 0.5-1 part by weight of surfactant, 2-3 parts by weight of dispersant, 40-60 parts by weight of solvent, 3-5 parts by weight of triethanolamine and 5.0-9.0 parts by weight of formic acid.
3. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 1, wherein the preparation method of the dimethylamino methyl phenyl triazole Mannich base comprises the following steps: adding benzotriazole, benzaldehyde and dimethylamine in a molar ratio of 3:2:3 into a reaction bottle, and uniformly mixing; dropwise adding hydrochloric acid to adjust the pH value of the mixed solution to 4, heating to 90 ℃, reacting for 4 hours, and distilling to obtain a crude product; mixing the obtained crude product and absolute ethyl alcohol according to the proportion of 1: adding 4 volumes of the precipitate into a beaker to obtain a white precipitate product, standing for precipitation, removing a layer solution, continuously washing and filtering the white precipitate product with absolute ethyl alcohol for 2-3 times, and finally vacuum-drying the obtained precipitate product for 5 hours for later use.
4. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 1, wherein the preparation method of 1, 3-dichloropyridine-2-hydroxypropane is as follows: adding 20 wt.% of HCl and quinoline with a molar ratio of 1: 2-2.1 into a reaction bottle, stirring and reacting at 60 ℃ for 1h, then sequentially dropwise adding epoxy chloropropane and quinoline into the reaction liquid, wherein the molar ratio of epoxy chloropropane to quinoline is 1: 1-1.1, continuing to react for 4h, and cooling to room temperature to obtain a crude product; extracting the crude product with petroleum ether, and removing petroleum ether solvent and insoluble substances in the solution by reduced pressure distillation to obtain reddish brown liquid, namely 1, 3-dichloropyridine-2-hydroxypropane.
5. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor as claimed in claim 2, wherein the synergist is a mixture of propiolic alcohol and potassium iodide, and the weight ratio of propiolic alcohol to potassium iodide is 3-7: 1-2.
6. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 2, wherein the surfactant is sodium dodecyl benzene sulfonate.
7. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 2, wherein the solvent is a mixed solution of methanol and polypropylene glycol-400, and the weight ratio of the two is 2-5: 1-2.
8. The pyridine derivative and Mannich base composite high-temperature acidification corrosion inhibitor according to claim 2, wherein the dispersant is a mixture of OP-10 and peregal O, and the weight ratio of the OP-10 to the peregal O is 1-2: 1-1.5.
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| CN115785932A (en) * | 2022-11-09 | 2023-03-14 | 中石化石油工程技术服务有限公司 | Lactic acid acidification corrosion inhibitor and preparation method thereof |
| CN115785932B (en) * | 2022-11-09 | 2023-11-14 | 中石化石油工程技术服务有限公司 | Lactic acid acidification corrosion inhibitor and preparation method thereof |
| CN115820237A (en) * | 2022-12-14 | 2023-03-21 | 泰坦(天津)能源技术有限公司 | Corrosion inhibitor for carbon dioxide flooding and preparation method thereof |
| CN115820237B (en) * | 2022-12-14 | 2024-02-06 | 泰坦(天津)能源技术有限公司 | Corrosion inhibitor for carbon dioxide flooding and preparation method thereof |
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