CN107190265A - A kind of compound imidazoline inhibitor and preparation method thereof - Google Patents
A kind of compound imidazoline inhibitor and preparation method thereof Download PDFInfo
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- CN107190265A CN107190265A CN201710322690.6A CN201710322690A CN107190265A CN 107190265 A CN107190265 A CN 107190265A CN 201710322690 A CN201710322690 A CN 201710322690A CN 107190265 A CN107190265 A CN 107190265A
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- imidazolinium compounds
- imidazoline
- water
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
The invention discloses a kind of compound imidazoline inhibitor, mixed by 20% 30% imidazolinium compounds II and the ethylene glycol and water of 20% 30% imidazolinium compounds III, 5%.Compound oil-water mixture system of the imidazoline inhibitor suitable for oilfield exploitation, production and storage and transport process of the present invention, has good corrosion inhibition concurrently under pure carbon dioxide environment and under hydrogen sulfide and carbon dioxide coexisted environment, can efficiently suppress H2S、CO2Corrode with caused by salt etc..
Description
Technical field
The invention belongs to oil field chemical field, specifically related to a kind of compound imidazoline inhibitor and preparation method thereof.
Background technology
Always along with the generation of metal erosion in oil extraction, production and storage and transport process, from oil transmission line to life
Production. art equipment all can be by different degrees of metal erosion, and they bring huge potential safety hazard to oil field steady production,
Serious meeting causes oil transmission line corrosion failure, causes severe environmental pollution.The main cause that corrosion occurs is that profit is mixed
Close H contained in liquid2S、CO2With the direct erosion of the corrosive medium such as high salt, the gold such as electrochemical corrosion, hydrogen embrittlement caused by
Category corrosion.
Corrosion inhibiter control metal erosion is the effective method that oilfield exploitation industry is generally used, wherein using most wide
The general and most significant corrosion inhibiter that produces effects is imidazoline corrosion inhibitor.But, currently used imidazoline corrosion inhibitor is generally applicable
The corrosive environment under system coexists in hydrogen sulfide and carbon dioxide.At present, the typical case that occurs is in the production of oil field：Crude oil is adopted
Go out end and be in pure carbon dioxide corrosive environment, during Crude Oil Transportation, production and storage, due to the growth of sulfate reducing bacteria
Hydrogen sulfide is produced, so as to cause the corruption that hydrogen sulfide and carbon dioxide coexist occur in production system, feed-line and storage cabin
Erosion, therefore, the corrosion inhibiter for being respectively provided with efficient performance researched and developed under both environment have important actual application value.
The content of the invention
Can not be under pure carbon dioxide environment and ring coexists in hydrogen sulfide and carbon dioxide for existing imidazoline corrosion inhibitor
There is the limitation of good corrosion inhibition simultaneously under border.
The present invention carries out the etherification reaction of the quaternary ammoniated and imidazoline of imidazoline respectively, and first the synthesis of selectivity is with two
The quaternary amine of individual imidazoline ring enhances the corrosion inhibition of the product under hydrogen sulfide and carbon dioxide coexisted environment, passes through selectivity
Imidazoline etherification reaction synthesized it is a kind of under pure carbon dioxide environment with excellent corrosion inhibition imidazoline etherificate derive
Thing, and compound synergic research is carried out on this basis, a kind of compound imidazoline inhibitor is prepared for, above two can be solved
Metal erosion problem under varying environment, has general applicability, it is to avoid use two in oil extraction, production and storage and transport process
Different corrosion inhibiter are planted, there is important actual application value to oil field steady production.
A kind of compound imidazoline inhibitor, it is characterized in that by imidazolinium compounds II and imidazolinium compounds III, ethylene glycol
Mixed with water；The percentage by weight of imidazolinium compounds II is 20%-30%, the percentage by weight of imidazolinium compounds III
It is 5% for 20%-30%, ethylene glycol percentage by weight, remaining is water；
Above-mentioned imidazolinium compounds II is the quaternary amine of many imidazolines, and its formula is：
Above-mentioned imidazolinium compounds III is the derivative after imidazoline etherificate, and its formula is：
Wherein R is one kind in pentadecyl, heptadecyl, 17 alkenyls, cyclohexenyl group, phenyl, preferably 17 alkenyls；
N is 2,3,4 or 5.
Present invention also offers the preparation method of above-mentioned compound quinoline corrosion inhibiter, including step are as follows：
1) by imidazoline chemical combination chemical compounds I and double (chloromethyl) benzene of 1,4- according to 1.8-2.2：1 mol ratio is added to dress
In the pyroreaction kettle for having stirring, condenser, water knockout drum and thermometer, proper catalyst is added, leads to N2Air in exclusion system,
Open and stir and gradually heat up, control temperature is reacted 2-3 hours at 135-140 DEG C, obtains imidazolinium compounds II；
Catalyst is：Potassium hydroxide, sodium hydroxide, sodium methoxide；
2) imidazolinium compounds I and expoxy propane reaction generation imidazolinium compounds III
In the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, proper catalyst is added, leads to N2Row
Except air in system, by imidazoline chemical combination chemical compounds I and expoxy propane according to 1：4-6 mol ratio is added in reactor, control
Temperature processed is reacted 2-4 hours at 125-130 °, after release cooling, obtains imidazolinium compounds III；
Catalyst is：Potassium hydroxide, sodium hydroxide, sodium methoxide；
3) imidazolinium compounds II, imidazolinium compounds III, alcohol and water are compounded according to aforementioned proportion, and compound miaow is made
Oxazoline corrosion inhibiter.
The good water solubility of the compound imidazoline inhibitor of the present invention, under pure carbon dioxide environment and hydrogen sulfide and carbon dioxide
Have good corrosion inhibition under coexisted environment concurrently, effectively suppress the generation of metal erosion in oil recovery production process, with universality.
Embodiment
Technical scheme is described further with reference to specific embodiment.
Raw material involved in the present invention is the imidazoline being related in commercial goods or known compound, embodiment 1-3
Compound I is prepared using following methods oneself：
By polyethylene polyamine and organic acid according to 1.15-1.2：1 mol ratio is added to equipped with stirring, condenser, Fen Shui
In the pyroreaction kettle of device and thermometer, water entrainer dimethylbenzene is added, leads to N2Air in exclusion system, opens and stirs and gradually rise
Temperature, control temperature react 1.5-3 hour at 130-135 DEG C, is further continued for being warming up to 235 DEG C of insulations 2-3 hours, up to by diformazan
Benzene and unnecessary material are steamed and finished, and obtain imidazolinium compounds I.Wherein polyethylene polyamine is diethylenetriamine, triethylene four
One kind in amine, TEPA, pentaethylene hexamine, preferably triethylene tetramine；Organic acid is selected from laurate, stearic acid, 18
One kind in (carbon) olefin(e) acid, preferably 18 (carbon) olefin(e) acids.
Reaction equation is as follows：
Embodiment 1
Step one
By triethylene tetramine and 18 (carbon) olefin(e) acids according to 1.2：1 mol ratio is added to equipped with stirring, condenser, Fen Shui
In the pyroreaction kettle of device and thermometer, water entrainer dimethylbenzene 60g is added, leads to air in N2 exclusion systems, stirring and gradually is opened
Heating, control temperature is reacted 2 hours at 135 DEG C, is further continued for being warming up to 235 DEG C and is incubated 3 hours, until by dimethylbenzene and unnecessary
Material, which is steamed, to be finished, and obtains imidazolinium compounds I.
Step 2
By double (chloromethyl) benzene of the imidazoline chemical combination chemical compounds I and 1,4- that are obtained in step one according to 2.1：1 mol ratio
It is added in the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, adds proper amount of methanol sodium as catalyst,
Air in logical N2 exclusion systems, is opened and stirs and gradually heat up, and control temperature is reacted 2 hours at 135-140 DEG C, obtains imidazoline
Compound ii.
Step 3
In the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, add proper amount of methanol sodium and be used as catalysis
Agent, leads to air in N2 exclusion systems, by the imidazoline chemical combination chemical compounds I and expoxy propane that are obtained in step one according to 1：4 rub
You are added in reactor ratio, and control temperature is reacted 2 hours at 125-130 DEG C, after release cooling, obtain imidazolinium compounds
Ⅲ。
Step 4:Imidazolinium compounds II 20%, imidazolinium compounds III 30%, ethylene glycol 5% and water 45% are compounded, i.e.,
Obtain compound imidazoline inhibitor 1.
Embodiment 2
Step one
By diethylenetriamine and laurate according to 1.15：1 mol ratio be added to equipped with stirring, condenser, water knockout drum and
In the pyroreaction kettle of thermometer, water entrainer dimethylbenzene 60g is added, leads to N2Air in exclusion system, opens and stirs and gradually heat up,
Control temperature react 2 hours at 130-135 DEG C, is further continued for being warming up to 235 DEG C and is incubated 2-3 hour, up to by dimethylbenzene with it is many
Remaining material, which is steamed, to be finished, and obtains imidazolinium compounds I.
Step 2
By double (chloromethyl) benzene of the imidazoline chemical combination chemical compounds I and 1,4- that are obtained in step one according to 2.1：1 mol ratio
It is added in the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, adds proper amount of methanol sodium as catalyst,
Logical N2Air in exclusion system, is opened and stirs and gradually heat up, and control temperature is reacted 2 hours at 135-140 DEG C, obtains imidazoline
Compound ii.
Step 3
In the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, add proper amount of methanol sodium and be used as catalysis
Agent, leads to N2Air in exclusion system, by the imidazoline chemical combination chemical compounds I and expoxy propane that are obtained in step one according to 1：6 rub
You are added in reactor ratio, and control temperature is reacted 2 hours at 125-130 DEG C, after release cooling, obtain imidazolinium compounds
Ⅲ。
Step 4:
Imidazolinium compounds II 30%, imidazolinium compounds III 20%, ethylene glycol 5% and water 45% are compounded, that is, are answered
Close imidazoline inhibitor 2.
Embodiment 3
Step one
By TEPA and 18 (carbon) olefin(e) acids according to 1.15：1 mol ratio is added to equipped with stirring, condenser, divided
In the pyroreaction kettle of hydrophone and thermometer, water entrainer dimethylbenzene 60g is added, leads to N2Air in exclusion system, open stirring and by
Edged up temperature, and control temperature react 2 hours at 130-135 DEG C, is further continued for being warming up to 235 DEG C and is incubated 2-3 hours, up to by diformazan
Benzene and unnecessary material are steamed and finished, and obtain imidazolinium compounds I.
Step 2
By double (chloromethyl) benzene of the imidazoline chemical combination chemical compounds I and 1,4- that are obtained in step one according to 2.1：1 mol ratio
It is added in the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, adds proper amount of methanol sodium as catalyst,
Logical N2Air in exclusion system, is opened and stirs and gradually heat up, and control temperature is reacted 2 hours at 135-140 DEG C, obtains imidazoline
Compound ii.
Step 3
In the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, add proper amount of methanol sodium and be used as catalysis
Agent, leads to N2Air in exclusion system, by the imidazoline chemical combination chemical compounds I and expoxy propane that are obtained in step one according to 1：4 rub
You are added in reactor ratio, and control temperature is reacted 2 hours at 125-130 DEG C, after release cooling, obtain imidazolinium compounds
Ⅲ。
Step 4:
Imidazolinium compounds II 25%, imidazolinium compounds III 25%, ethylene glycol 5% and water 45% are compounded, that is, are answered
Close imidazoline inhibitor 3.
The inhibition evaluation test in the case where system coexists in hydrogen sulfide and carbon dioxide：
Experiment condition：Temperature：75℃；Test piece material：Q235 steel；Time：24hr；Carbon dioxide partial pressure：0.8MPa；Vulcanization
Hydrogen dividing potential drop：0.7KPa；10% crude oil；Test water quality, such as following table.
Test water quality table
| Project | Unit | Numerical value |
| Na++K+ | mg/l | 12474 |
| Ca2+ | mg/l | 551 |
| Mg2+ | mg/l | 190 |
| Cl- | mg/l | 19178 |
| HCO3 - | mg/l | 2330 |
| CO3 2- | mg/l | 180 |
| SO4 2- | mg/l | 16 |
Experimental method：According to SY-T5273-2000《Oil field extracted water corrosion inhibiter method of evaluating performance》Mesohigh dynamic
Corrosion rate and corrosion inhibition rate assay method.
Note：1 be the imidazolinium compounds II for preparing in embodiment 1-3, and corrosion inhibition is optimal, specially in embodiment 2
Imidazolinium compounds II；
2 be the imidazolinium compounds III for preparing in embodiment 1-3, and corrosion inhibition is optimal, specially in embodiment 2
Imidazolinium compounds III.
Inhibition evaluation experimental under pure carbon dioxide system：
Experiment condition：Temperature：75℃；Test piece material：Q235 steel；Time：24hr；Pressure carbon dioxide：0.8MPa；10%
Crude oil；Water quality is tested, the water quality table in one is tested with corrosion inhibiter.
Experimental method：According to SY-T5273-2000《Oil field extracted water corrosion inhibiter method of evaluating performance》Mesohigh dynamic
Corrosion rate and corrosion inhibition rate assay method.
Note：1 be the imidazolinium compounds II for preparing in embodiment 1-3, and corrosion inhibition is optimal, specially in embodiment 2
Imidazolinium compounds II；
2 be the imidazolinium compounds III for preparing in embodiment 1-3, and corrosion inhibition is optimal, specially in embodiment 2
Imidazolinium compounds III.
Claims (3)
1. a kind of compound imidazoline inhibitor, it is characterized in that by imidazolinium compounds II and imidazolinium compounds III, ethylene glycol and
Water is mixed；The percentage by weight of imidazolinium compounds II is 20%-30%, and the percentage by weight of imidazolinium compounds III is
20%-30%, the percentage by weight of ethylene glycol are 5%, and remaining is water；
Wherein described imidazolinium compounds II is the quaternary amine of many imidazolines, and its formula is：
Described imidazolinium compounds III is the derivative after imidazoline etherificate, and its formula is：
Wherein R is one kind in pentadecyl, heptadecyl, 17 alkenyls, cyclohexenyl group, phenyl；N is 2,3,4 or 5.
2. compound imidazoline inhibitor according to claim 1, it is characterised in that described R is 17 alkenyls.
3. a kind of preparation method of the compound imidazoline inhibitor described in claim 1, including step are as follows：
1) by imidazoline chemical combination chemical compounds I and double (chloromethyl) benzene of 1,4- according to 1.8-2.2：1 mol ratio is added to be equipped with and stirred
Mix, in the pyroreaction kettle of condenser, water knockout drum and thermometer, add proper catalyst, lead to N2Air in exclusion system, opens and stirs
Mix and gradually heat up, control temperature is reacted 2-3 hours at 135-140 DEG C, obtains imidazolinium compounds II；
Catalyst is：Potassium hydroxide, sodium hydroxide, sodium methoxide；
2) imidazolinium compounds I and expoxy propane reaction generation imidazolinium compounds III
In the pyroreaction kettle equipped with stirring, condenser, water knockout drum and thermometer, proper catalyst is added, leads to N2Exclusion system
Interior air, by imidazoline chemical combination chemical compounds I and expoxy propane according to 1：4-6 mol ratio is added in reactor, controls temperature
Reacted 2-4 hours at 125-130 °, after release cooling, obtain imidazolinium compounds III；
Catalyst is：Potassium hydroxide, sodium hydroxide, sodium methoxide；
3) imidazolinium compounds II, imidazolinium compounds III, ethylene glycol and water are answered according to the ratio described in claim 1
Match somebody with somebody, compound imidazoline inhibitor is made.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107829094A (en) * | 2017-11-02 | 2018-03-23 | 中国石油化工股份有限公司 | Sulfur resistive high temperature resistant corrosion inhibitor and preparation method thereof |
| CN109609110A (en) * | 2018-11-29 | 2019-04-12 | 中国石油天然气股份有限公司 | A kind of CO2Displacement of reservoir oil inhibition descaling agent and preparation method and application method |
-
2017
- 2017-05-09 CN CN201710322690.6A patent/CN107190265A/en active Pending
Non-Patent Citations (3)
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| 李家俊等: "一种非离子型缓蚀剂的合成及其性能研究", 《工业水处理》 * |
| 李家俊等: "双咪唑啉缓蚀剂的合成与性能研究", 《工业水处理》 * |
| 杨浩波等: "一种高温缓蚀剂在海上油田的应用", 《广州化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107829094A (en) * | 2017-11-02 | 2018-03-23 | 中国石油化工股份有限公司 | Sulfur resistive high temperature resistant corrosion inhibitor and preparation method thereof |
| CN107829094B (en) * | 2017-11-02 | 2019-10-11 | 中国石油化工股份有限公司 | High temperature resistant corrosion inhibitor and preparation method thereof |
| CN109609110A (en) * | 2018-11-29 | 2019-04-12 | 中国石油天然气股份有限公司 | A kind of CO2Displacement of reservoir oil inhibition descaling agent and preparation method and application method |
| CN109609110B (en) * | 2018-11-29 | 2021-03-09 | 中国石油天然气股份有限公司 | CO (carbon monoxide)2Corrosion and scale inhibitor for oil displacement, preparation method and use method thereof |
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Application publication date: 20170922 |