CN104513204B - It is a kind of to contain three key bi-imidazoline class compounds and the preparation method containing three key bi-imidazoline class carbon dioxide corrosion inhibitors and carbon dioxide corrosion inhibitor - Google Patents
It is a kind of to contain three key bi-imidazoline class compounds and the preparation method containing three key bi-imidazoline class carbon dioxide corrosion inhibitors and carbon dioxide corrosion inhibitor Download PDFInfo
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- CN104513204B CN104513204B CN201310446440.5A CN201310446440A CN104513204B CN 104513204 B CN104513204 B CN 104513204B CN 201310446440 A CN201310446440 A CN 201310446440A CN 104513204 B CN104513204 B CN 104513204B
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- carbon dioxide
- dioxide corrosion
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- 238000005260 corrosion Methods 0.000 title claims abstract description 57
- 230000007797 corrosion Effects 0.000 title claims abstract description 55
- -1 bi-imidazoline class compounds Chemical class 0.000 title claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 26
- 239000003112 inhibitor Substances 0.000 title claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- DZPXBTZJEFYBBK-UHFFFAOYSA-N 1-(4,5-dihydroimidazol-1-yl)-4,5-dihydroimidazole Chemical class C1=NCCN1N1C=NCC1 DZPXBTZJEFYBBK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 241001272567 Hominoidea Species 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000011938 amidation process Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims 1
- 125000005233 alkylalcohol group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000010962 carbon steel Substances 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- 238000009434 installation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003129 oil well Substances 0.000 abstract description 3
- VKFAUCPBMAGVRG-UHFFFAOYSA-N dipivefrin hydrochloride Chemical compound [Cl-].C[NH2+]CC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 VKFAUCPBMAGVRG-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 0 C*N1C(*C2=NCCN2*CC#C)=NCC1 Chemical compound C*N1C(*C2=NCCN2*CC#C)=NCC1 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- URLVCROWVOSNPT-XOTOMLERSA-N (2s)-4-[(13r)-13-hydroxy-13-[(2r,5r)-5-[(2r,5r)-5-[(1r)-1-hydroxyundecyl]oxolan-2-yl]oxolan-2-yl]tridecyl]-2-methyl-2h-furan-5-one Chemical compound O1[C@@H]([C@H](O)CCCCCCCCCC)CC[C@@H]1[C@@H]1O[C@@H]([C@H](O)CCCCCCCCCCCCC=2C(O[C@@H](C)C=2)=O)CC1 URLVCROWVOSNPT-XOTOMLERSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QUHYUSAHBDACNG-UHFFFAOYSA-N acerogenin 3 Natural products C1=CC(O)=CC=C1CCCCC(=O)CCC1=CC=C(O)C=C1 QUHYUSAHBDACNG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- URLVCROWVOSNPT-QTTMQESMSA-N desacetyluvaricin Natural products O=C1C(CCCCCCCCCCCC[C@@H](O)[C@H]2O[C@@H]([C@@H]3O[C@@H]([C@@H](O)CCCCCCCCCC)CC3)CC2)=C[C@H](C)O1 URLVCROWVOSNPT-QTTMQESMSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D233/16—Radicals substituted by nitrogen atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Contain three key bi-imidazoline class compounds and preparation method containing three key bi-imidazoline class carbon dioxide corrosion inhibitors and carbon dioxide corrosion inhibitor the present invention relates to a kind of, including：Containing three key bi-imidazoline compounds, nonionic surfactant, low molecular alcoholic solvents.The corrosion inhibiter is used for the carbonated oil well of oil gas field, gas well, surface gathering and transferring pipeline, and the corrosion protection of water treatment system equipment installation.The present invention uses dehydration, molecule inner dewatering reaction between dicarboxylic acids and polyamine molecule; with further being reacted containing three key compounds; generation contains three key bi-imidazoline compounds; there is more preferable protective effect to carbon steel containing two phenodiazine five-ring heterocycles, containing multiple activated adoption centers such as triple bonded group, the organic adsorption film of formation in molecule.Corrosion inhibiter provided by the invention has good water solubility in high salinity oil gas field production fluid, without just can dissolve with low mass molecule alcohol equal solvent is scattered.The carbon dioxide corrosion inhibitor, corrosion inhibition is good, compatibility is good, soluble in water.
Description
Technical field
The invention belongs to corrosion protection technology field, more particularly to one kind is containing three key bi-imidazoline class compounds and containing three keys
The preparation method of bi-imidazoline class carbon dioxide corrosion inhibitor and carbon dioxide corrosion inhibitor.
Background technology
In the recovery process of petroleum gas, Oil/gas Well corrosion essentially relates to all corrosion types, but H2S corrodes
And CO2Corrosion is the most common Corrosion Types that Oil/gas Well runs into.It is a kind of effective corrosion protection steps to add corrosion inhibiter, especially
It is to contain CO in height2、H2In the recovery process of the acid oil gas such as S, the preventing and treating of sour gas corrosion destruction is carried out using corrosion inhibiter.
Current corrosion inhibiter employed both at home and abroad is essentially all adsorption corrosion inhibitor, such as chain organic amine and its derivative
Thing, imidazoline and its salt or imidazolidine derivatives quaternary ammonium salts, rosin amine derivative；Other organic compound (sulfonate, imines
Acetogenin and alkynol class).Generally believe organic amine, organic amine salt, imidazolidine derivatives, quaternary ammonium salt corrosion mitigating effect compared with
It is good.
Conventional imidazoline, amide-type corrosion inhibiter are generally water-soluble poor, even if having carried out water-soluble transformation or optimization (such as
It is quaternized etc.), due to containing acid amides or amine groups in its molecular structure, at the scene during use, often with organophosphor acids
Antisludging agent, the suppression oil gas field chemical addition agent such as salt agent are incompatible, phenomena such as easily producing layering and precipitating, have a strong impact on various medicaments
Using effect.Therefore, the corrosion inhibiter that at the scene during use, compatibility is good, wide adaptability, corrosion inhibition are excellent more can
Good corrosion protection effect is enough played, while nor affects on the performance of other chemical agents.
The content of the invention
The present invention is in order to solve the above problems, there is provided a kind of preparation method is simple, and corrosion mitigating effect and water solubility are preferable
Preparation containing three key bi-imidazoline class compounds and containing three key bi-imidazoline class carbon dioxide corrosion inhibitors and carbon dioxide corrosion inhibitor
Method.
The present invention is to be achieved through the following technical solutions：
One kind contains three key bi-imidazoline class compounds, including containing three key bi-imidazoline class compounds there is following structure to lead to
Formula：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.
One kind contains three key bi-imidazoline class carbon dioxide corrosion inhibitors, including following components：
Containing three key bi-imidazoline compound 40-60 weight %；
Nonionic surfactant 3-5 weight %；
Low molecular alcoholic solvents 46-57 weight %；
Wherein, there is following general structure containing three key bi-imidazoline compounds：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.
Described nonionic surfactant is AEO or APES；Wherein, it is described
APEO OP values be 10；The low molecular alcoholic solvents are methanol, ethanol.
A kind of preparation method for containing three key bi-imidazoline class carbon dioxide corrosion inhibitors, it is characterised in that comprise the following steps：
Step 1：Preparation contains three key bi-imidazoline class compounds：
It is 1.0 to add mol ratio in certain sequence in the reactor：1.5~2.5 binary organic carboxyl acid and polyamines, is stirred
Mix, be warming up to 110-150 DEG C under agitation and start to flow back, maintain the reflux for 1.0~2.0h；140~180 DEG C are warming up to again,
3.0~the 6.0h that flows back carries out amidation process；It is continuously heating to 220~280 DEG C of backflow 3.0-10.0h and carries out cyclization, obtains
To bi-imidazoline intermediate；Bi-imidazoline intermediate temperature is down to 70-100 DEG C, according to mol ratio bi-imidazoline intermediate：Contain
Compound=1.0 of three keys：1.5-2.5, which is added, contains three key compounds, then is warming up to 100-150 DEG C, continues to react 3.0-
6.0h, obtains the homogeneous thick liquid of brown color, as target product-contain three key bi-imidazoline compounds, standby；
Step 2：Weighed respectively according to mass percent containing three key bi-imidazoline compounds, nonionic surfactant and low
Molecule alcoholic solvent, three key bi-imidazoline compounds will be contained and mutually mixed with nonionic surfactant, low molecular alcoholic solvents, stirred
Uniformly, that is, obtain containing three key bi-imidazoline class carbon dioxide corrosion inhibitors.
The binary organic carboxyl acid is：Adipic acid or decanedioic acid.
The polyamines is：Diethylenetriamine, triethylene tetramine, TEPA or polyethylene polyamine.
Three key compounds that contain are propine chlorine.
Described nonionic surfactant is AEO or APES；Wherein, it is described
APEO OP values be 10；The low molecular alcoholic solvents are methanol, ethanol.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention uses dehydration, molecule inner dewatering reaction between dicarboxylic acids and polyamine molecule, with entering one containing three key compounds
Step reaction, generation contain three key bi-imidazoline compounds, and two phenodiazine five-ring heterocycles, multiple containing triple bonded group etc. are contained in molecule
Activated adoption center, the organic adsorption film of formation have more preferable protective effect to carbon steel.
Corrosion inhibiter provided by the invention has good water solubility in high salinity oil gas field production fluid, without with low point
Sub- alcohol equal solvent is scattered just to be can dissolve.
Corrosion inhibiter provided by the present invention can be used for the carbonated oil well of oil gas field, gas well, surface gathering and transferring pipeline, with
And the corrosion protection of water treatment system equipment installation.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
It is 1.0 to add mol ratio in certain sequence in the reactor：1.5 decanedioic acid, diethylenetriamine, in stirring condition
Under be warming up to 110 DEG C, now there is liquid to separate, maintain the reflux for 1h；140 DEG C are warming up to again, and backflow 3h carries out amidation process；
It is continuously heating to 280 DEG C of backflow 3h and carries out cyclization, obtains bi-imidazoline intermediate；
Bi-imidazoline intermediate temperature is down to 70 DEG C, according to mol ratio bi-imidazoline intermediate：Propine chlorine=1.0：1.5
Propine chlorine is added, then is warming up to 100 DEG C, continues to react 3h, obtains the homogeneous thick liquid of brown color, as target product-contain three
Key bi-imidazoline compound.
It is by content：Containing three key bi-imidazolines：40 weight %, OP-10：3.0 weight %, ethanol：57 weight %, mutually
Mixing, stirs.Preferably take high, medium and low three values of value range.Wherein, OP values are AEO or alkyl
The OP values of phenol polyethenoxy ether.
Embodiment 2
It is 1.0 to add mol ratio in certain sequence in the reactor：1.7 adipic acid, triethylene tetramine, in stirring condition
Under be warming up to 120 DEG C, now there is liquid to separate, maintain the reflux for 1.4h；160 DEG C are warming up to again, and it is anti-that backflow 4h carries out amidatioon
Should；It is continuously heating to 260 DEG C of backflow 4.5h and carries out cyclization, obtains bi-imidazoline intermediate.
Bi-imidazoline intermediate temperature is down to 85 DEG C, according to mol ratio bi-imidazoline intermediate：Propine chlorine=1.0：1.8
Propine chlorine is added, then is warming up to 130 DEG C, continues to react 4h, obtains the homogeneous thick liquid of brown color, as target product-contain three
Key bi-imidazoline compound.
It is by content：Containing three key bi-imidazolines：45 weight %, OP-10：3.5 weight %, methanol：51.5 weight %, mutually
Mix, stir.
Embodiment 3
It is about 1.0 to add mol ratio in certain sequence in the reactor：2.05 decanedioic acid, TEPA, are being stirred
Under the conditions of be warming up to 135 DEG C, now there is liquid to separate, maintain the reflux for 1.8h；170 DEG C are warming up to again, and backflow 5h carries out amidatioon
Reaction；It is continuously heating to 240 DEG C of backflow 6h and carries out cyclization, obtains bi-imidazoline intermediate.
Bi-imidazoline intermediate temperature is down to 90 DEG C, according to mol ratio bi-imidazoline intermediate：Propine chlorine=1.0：1.7
Ratio adds propine chlorine, then is warming up to 145 DEG C, continues to react 5h, obtains the homogeneous thick liquid of brown color, as target product-
Containing three key bi-imidazoline compounds.
It is by content：Containing three key bi-imidazolines：50 weight %, OP-10：4.0 weight %, methanol：46 weight %, mutually
Mixing, stirs.
Embodiment 4
It is about 1.0 to add mol ratio in certain sequence in the reactor：2.5 adipic acid, polyethylene polyamine, in stirring bar
150 DEG C are warming up under part, now has liquid to separate, maintains the reflux for 2h；180 DEG C are warming up to again, and it is anti-that backflow 6h carries out amidatioon
Should；It is continuously heating to 220 DEG C of backflow 10h and carries out cyclization, obtains bi-imidazoline intermediate.
Bi-imidazoline intermediate temperature is down to 100 DEG C, according to mol ratio polyamines：Propine chlorine=1.0：2.5 add propine
Chlorine, then be warming up to 160 DEG C, continue to react 6h, obtain the homogeneous thick liquid of brown color, as target product-containing the double imidazoles of three keys
Quinoline compound.
It is by content：Containing three key bi-imidazolines (embodiment 4)：60 weight %, OP-10：5 weight %, methanol：52 weights
% is measured, mutually mixes, stirs.
Embodiment 5
In order to examine the present invention containing three key bi-imidazoline class carbon dioxide corrosion inhibitors in CO2Corrosion inhibition in environment, enters
Experimental evaluation is gone.Test piece is N80, and test medium is formulated by analysis pure chemistry reagent and redistilled water, and its composition is shown in
Table 1：
Table 1
After test medium prepares, high-purity N logical first2More than deoxygenation 12h, then lead to CO21h, last solution clarification are standby
With.
By the test piece of N80 steel corrosions (size 71.00mm × 12.92mm × 1.50mm), with abrasive paper for metallograph sanding and polishing step by step,
Make its finish of each surface and rib, angle, hole everywhere consistent, then with distilled water flushing, acetone degreasing is dry after deoiling to weigh
It is standby.When carrying out corrosion weight loss experiment test, the test piece handled well is immersed in CO2(temperature in the simulation oil field aqueous medium of saturation
Degree control is at 80 ± 1 DEG C) after closed lacing film 168h, test piece is taken out, removes corrosion product, is dried after distilled water and acetone cleaning
To constant weight, coupon weight is accurately weighed.Corrosion rate is calculated by the weight loss of test piece before and after corrosion experiment and added three keys that contain are double
The inhibition efficiency of imidazoline inhibitor.
Table 2
One kind contains three key bi-imidazoline class compounds, including containing three key bi-imidazoline class compounds there is following structure to lead to
Formula：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.Wherein, in molecule containing two phenodiazine five-ring heterocycles,
Containing multiple activated adoption centers such as triple bonded group, the organic adsorption film of formation has more preferable protective effect to carbon steel.
One kind contains three key bi-imidazoline class carbon dioxide corrosion inhibitors, the corrosion inhibiter by its it is total on the basis of contain：
Containing three key bi-imidazoline quaternary ammonium salt 40-60 weight %；
Nonionic surfactant 3-5 weight %；
Low molecular alcoholic solvents 46-57 weight %；
Wherein, there is following general structure containing three key bi-imidazoline compounds：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.
Further, the nonionic surfactant is AEO or APES；Wherein,
The OP values of described APEO are 10.
Further, the low molecular alcoholic solvents are methanol, ethanol, isopropanol or ethylene glycol.
The present invention uses dehydration, molecule inner dewatering reaction between dicarboxylic acids and polyamine molecule, with entering one containing three key compounds
Step reaction, generation contain three key bi-imidazoline compounds, and two phenodiazine five-ring heterocycles, multiple containing triple bonded group etc. are contained in molecule
Activated adoption center, the organic adsorption film of formation have more preferable protective effect to carbon steel.
Corrosion inhibiter provided by the invention has good water solubility in high salinity oil gas field production fluid, without with low point
Sub- alcohol equal solvent is scattered just to be can dissolve.
Corrosion inhibiter provided by the present invention can be used for the carbonated oil well of oil gas field, gas well, surface gathering and transferring pipeline, with
And the corrosion protection of water treatment system equipment installation.
Carbon dioxide corrosion inhibitor of the present invention includes：(A) containing three key bi-imidazoline compounds, (B) nonionic surfactant,
(C) low molecular alcoholic solvents.Carbon dioxide corrosion inhibitor provided by the present invention, corrosion inhibition is good, compatibility is good, soluble in water.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (5)
1. one kind contains three key bi-imidazoline class compounds, it is characterised in that described has containing three key bi-imidazoline class compounds
Following general structure：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.
2. one kind contains three key bi-imidazoline class carbon dioxide corrosion inhibitors, it is characterised in that including following components：
Containing three key bi-imidazoline compound 40-60 weight %；
Nonionic surfactant 3-5 weight %；
Low molecular alcoholic solvents 46-57 weight %；
Wherein, there is following general structure containing three key bi-imidazoline compounds：
R in formula is the straight chained alkyl that amount of carbon atom is 4 or 8.
3. according to claim 2 contain three key bi-imidazoline class carbon dioxide corrosion inhibitors, it is characterised in that it is described it is non-from
Sub- surfactant is AEO or APES；Wherein, the OP values of described APEO
For 10；The low molecular alcoholic solvents are methanol, ethanol.
4. a kind of preparation method containing three key bi-imidazoline class carbon dioxide corrosion inhibitors prepared described in claim 2, its feature
It is, comprises the following steps：
Step 1：Preparation contains three key bi-imidazoline class compounds：
It is 1.0 to add mol ratio in certain sequence in the reactor：1.5~2.5 binary organic carboxyl acid and polyamines, stirring,
110-150 DEG C is warming up under stirring condition to start to flow back, and maintains the reflux for 1.0~2.0h；140~180 DEG C are warming up to again, backflow
3.0~6.0h carries out amidation process；It is continuously heating to 220~280 DEG C of backflow 3.0-10.0h and carries out cyclization, obtains double
Imidazoline intermediate；Bi-imidazoline intermediate temperature is down to 70-100 DEG C, according to mol ratio bi-imidazoline intermediate：Containing three keys
Compound=1.0：1.5-2.5, which is added, contains three key compounds, then is warming up to 100-150 DEG C, continues to react 3.0-6.0h, obtains
The homogeneous thick liquid of brown color, as target product-and contain three key bi-imidazoline compounds, it is standby；Wherein, the binary is organic
Carboxylic acid is：Adipic acid or decanedioic acid；The polyamines is：Diethylenetriamine；Three key compounds that contain are propine chlorine；
Step 2：Weighed respectively according to mass percent containing three key bi-imidazoline compounds, nonionic surfactant and low molecule
Alcoholic solvent, three key bi-imidazoline compounds will be contained and mutually mixed with nonionic surfactant, low molecular alcoholic solvents, stirring is equal
It is even, that is, obtain containing three key bi-imidazoline class carbon dioxide corrosion inhibitors.
5. preparation method according to claim 4, it is characterised in that described nonionic surfactant is poly alkyl alcohol
Oxygen vinethene or APES；Wherein, the OP values of described APEO are 10；The low molecular alcoholic solvents are
Methanol, ethanol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE653881A (en) * | 1963-10-04 | 1965-02-01 | ||
| US3187004A (en) * | 1961-05-01 | 1965-06-01 | Diamond Alkali Co | Halogenated alkyl and aryl substituted glycolurils |
| WO1996018684A1 (en) * | 1994-12-14 | 1996-06-20 | The Government Of The United States Of America, | Epoxy pipelining composition and method of manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3187004A (en) * | 1961-05-01 | 1965-06-01 | Diamond Alkali Co | Halogenated alkyl and aryl substituted glycolurils |
| BE653881A (en) * | 1963-10-04 | 1965-02-01 | ||
| WO1996018684A1 (en) * | 1994-12-14 | 1996-06-20 | The Government Of The United States Of America, | Epoxy pipelining composition and method of manufacture |
Non-Patent Citations (1)
| Title |
|---|
| 2 种癸二酸咪唑啉季铵盐的合成及缓蚀性能评价;亓树成，等;《应用化学》;20130715;第29卷(第7期);全文,尤其scheme1 * |
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