CN103556158A - Polyethylene glycol bridging cyclodextrin corrosion inhibitor and preparation method thereof - Google Patents
Polyethylene glycol bridging cyclodextrin corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN103556158A CN103556158A CN201310562650.0A CN201310562650A CN103556158A CN 103556158 A CN103556158 A CN 103556158A CN 201310562650 A CN201310562650 A CN 201310562650A CN 103556158 A CN103556158 A CN 103556158A
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Abstract
The invention relates to a polyethylene glycol bridging cyclodextrin corrosion inhibitor for preventing corrosion of steel pipelines of an oil-gas field and a preparation method of the polyethylene glycol bridging cyclodextrin corrosion inhibitor. The polyethylene glycol bridging cyclodextrin corrosion inhibitor can prevent the pipelines of the oil-gas field from being corroded to improve the economical efficiency and safety of oil production. The technical scheme is as follows: the corrosion inhibitor has a chemical name of polyethylene glycol bridging cyclodextrin. The preparation method of the corrosion inhibitor comprises the steps of firstly, adding polyethylene glycol and thionyl chloride to react for 7 hours at -10 DEG C so as to prepare chlorinated polyethylene glycol; then adding cyclodextrin into the product of the previous step, uniformly performing ultrasonic oscillation, then adding sodium hydroxide and sodium dodecylbenzene sulfonated as catalysts, and stirring to react for 7-8 hours at 60 DEG C under the protection of nitrogen, thereby preparing the polyethylene glycol bridging cyclodextrin. The preparation method of the polyethylene glycol bridging cyclodextrin is simple, mild in synthetic condition and simple in equipment, and the obtained product has good adsorbability and dispersity to steel pipelines, is high in corrosion inhibition efficiency, and is used for corrosion prevention of oil-gas field pipelines.
Description
Technical field
The present invention relates to a kind of polyoxyethylene glycol Cyclodextrin Bridged inhibiter and preparation method who prevents corrosion for oil-gas field steel pipeline.
Background technology
Pressure break and acidifying are the important method that improves oil-gas field recovery ratio.But well-drilling waste water and fracture acidizing waste water are oil and gas enterprise primary pollution source.At present, the technical development of water treatment is not also very perfect, and the acid ion containing in waste water and dissolved salt can corrode steel pipeline.Along with the growth of oilfield exploitation time and the continuous deterioration of water quality, cause the extent of corrosion of petroleum pipe line to be deepened, cause serious potential safety hazard and financial loss.
The anti-corrosion measure that oil field at home filling pipe system is mainly taked at present has: Chemical Preservation, coating protection, oxygen scavenger, sterilant, galvanic protection, protective nitride and employing frp pipe.Wherein adopting the inhibiter in Chemical Preservation is anticorrosion one of the most effective means of oil field equipment.In medium, add a small amount of inhibiter of people, can significantly reduce the corrosion speed of metallic substance, and can keep the physical and mechanical properties of metal constant.Inhibiter has that cost is low, simple to operate, instant effect, do not change plant machinery performance, be applicable to the features such as long-term protection.Therefore, adopting inhibiter to be undoubtedly one of optimized protection measure of oil-gas field equipment, is also maximum anti-corrosion measure of scholar's research both at home and abroad in this field.Oil-gas field rig-site utilization both domestic and external shows, the work-ing life that filling inhibiter can improve oil field equipment greatly.
Summary of the invention
The object of the invention is: for fear of oil-gas field pipeline, be corroded, improve economy and the security of recovering the oil, spy provides a kind of polyoxyethylene glycol Cyclodextrin Bridged inhibiter and preparation method.
In order to achieve the above object, the present invention adopts polyoxyethylene glycol bridging between cyclodextrin.Polyoxyethylene glycol stable in properties, can mix with multi-solvents, is important inhibiter and rust remover.In addition, cyclodextrin has the hydrophobic special construction of the hydrophilic inner chamber of exocoel, can adsorb with inclusion oil field waste in impurity, strengthened the corrosion mitigating effect of polyoxyethylene glycol to iron and steel.The chemical name of this Cyclodextrin Bridged inhibiter is polyoxyethylene glycol Cyclodextrin Bridged, and its structural formula is:
In formula, n represents that the polymerization degree of polyoxyethylene glycol is 8-22,
symbol represents that cyclodextrin is the structural unit of alpha-cylodextrin or beta-cyclodextrin.
The preparation method of inhibiter of the present invention mainly comprises two steps: (1) is first dissolved into the polyoxyethylene glycol of 0.015-0.02mol in the dimethyl sulfoxide solvent of 0-50ml, be placed in dry there-necked flask, under agitation condition, drip the sulfur oxychloride of 0.03-0.04mol, it is-10 ℃ that ice-water bath is controlled temperature of reaction, the temperature that drips reactor in sulfur oxychloride process remains on-10 ℃-0 ℃, reflux time is 7h, the faint yellow mixed solution of gained is placed on to the Rotary Evaporators distillation 48h in ventilating kitchen, remove the sour gas such as byproduct of reaction hydrogen sulfide and hydrochloric acid, make chloro polyoxyethylene glycol.(2) the chloro polyoxyethylene glycol upper step of 0.015-0.02mol being made and 0.03-0.04mol cyclodextrin are placed in ultrasonic stirrer and fully stir 20min.Reaction mixture is joined in the reactor that is connected with exhaust gas processing device, question response temperature adds the sodium hydroxide of reactant total mass 7-8% and the Sodium dodecylbenzene sulfonate of 0.2-0.3% to make catalyzer while being increased to 50 ℃ again.After finally above-mentioned solution being mixed, inflated with nitrogen 20min removes oxygen, controlling temperature of reaction is 60 ℃, the stirring reaction time is 7-8h, pour gained brown color mixed solution in beaker standing cooling 1h, with dilute hydrochloric acid, the solution obtaining is neutralized to pH=7, decompress filter is removed unreacted cyclodextrin.Again gained filtrate is washed 3-5 time with dehydrated alcohol, finally, gained solid dry 24h in the baking oven of 30 ℃, make white solid powder polyoxyethylene glycol Cyclodextrin Bridged.
Compared with prior art, the invention has the beneficial effects as follows: preparation method is simple and feasible for (1) polyoxyethylene glycol Cyclodextrin Bridged, reaction conditions is gentle; (2) asepsis environment-protecting, the raw material polyoxyethylene glycol that the present invention uses and cyclodextrin is all nontoxic can not pollute oil product; (3) to steel pipeline high adsorption capacity, inhibition efficiency is high.
Accompanying drawing explanation:
Fig. 1 is the infrared spectrogram of polyoxyethylene glycol Cyclodextrin Bridged inhibiter of the present invention.
Embodiment:
Below by embodiment, the present invention is further described.
Embodiment 1
The first step: prepare chloro poly(oxyethylene glycol) 400.
First by the poly(oxyethylene glycol) 400 solution of 21.5ml, (poly(oxyethylene glycol) 400 is liquid, 400 is its molecular-weight average, do not need with dmso solution) be placed in the there-necked flask that 250mL is dry, under agitation condition, drip the sulfur oxychloride of 8.72ml, it is-1 ℃ that ice-water bath is controlled temperature of reaction, and the temperature that drips reactor in sulfur oxychloride process remains on below 0 ℃.Reflux time is 7h, and the faint yellow mixed solution of gained is placed on to the Rotary Evaporators distillation 48h in ventilating kitchen, removes the sour gas such as byproduct of reaction hydrogen sulfide, hydrochloric acid, makes chloro poly(oxyethylene glycol) 400.
Second step: preparation poly(oxyethylene glycol) 400 bridging beta-cyclodextrin.
The chloro poly(oxyethylene glycol) 400 that the upper step of 6.6g is made and 34.05g beta-cyclodextrin (mol ratio is 1:2) are placed in ultrasonic stirrer and fully stir 20min.Again mixture is joined in the there-necked flask of the 250mL that is connected with exhaust gas processing device, question response temperature adds 7g sodium hydroxide and 0.1g Sodium dodecylbenzene sulfonate to make catalyzer while being increased to 50 ℃, after finally above-mentioned solution being mixed, inflated with nitrogen 20min removes oxygen, controlling temperature of reaction is 60 ℃, and reflux time is 7h, and the mixed solution that makes brown color is poured the standing 1h of beaker into, with hydrochloric acid, regulate pH=7 after cooling, decompress filter falls responseless beta-cyclodextrin.Again the filtrate obtaining is used to absolute ethanol washing (each 20ml) 4 times, finally, by the solid phase prod of gained dry 24h in the baking oven of 30 ℃, made purer white solid powder poly(oxyethylene glycol) 400 bridging beta-cyclodextrin inhibiter.
This research adopts infrared spectroscopy to carry out initial analysis to the various functional groups in polyoxyethylene glycol Cyclodextrin Bridged.With the Paragon100 type infrared spectrometer that KBr compressing tablet sample preparation ，Yi PE company produces, product is done to red analysis.
Main absorption peak is as follows:
3383cm
-1stretching vibration peak (because polyoxyethylene glycol Cyclodextrin Bridged is soluble in water, so contain-OH) for-OH; 1645cm
-1flexural vibration peak for the characteristic peak-OH of cyclodextrin; 1464cm
-1for-CH
2flexural vibration peak; 1155cm
-1and 858cm
-1flexible and the symmetrical stretching vibration peak of the unsymmetrically of be respectively-C-O-C of place, larger with respect to the ehter bond peak of polyoxyethylene glycol, illustrate that its hydroxyl is substituted to have generated ehter bond.
Embodiment 2
The infrared spectra of polyoxyethylene glycol Cyclodextrin Bridged
The infrared spectra of the poly(oxyethylene glycol) 400 bridging beta-cyclodextrin obtaining by embodiment 1 is shown in that Fig. 1 is learnt by spectrum analysis, and gained target product conforms to substantially with expection product.
Embodiment 3
Experiment material is Q235 carbon steel, and chemical constitution is (W%): C (0.14-0.22), Mn (0.30-0.65), and Si (≤0.30), S (≤0.05), P (≤0.045), that remaining is Fe.Corrosive medium is the hydrochloric acid soln of 0.5mol/L.Q235 carbon steel is immersed in respectively in the polyoxyethylene glycol Cyclodextrin Bridged inhibiter that adds different concns, and temperature is 25 ℃, and pressure is normal pressure.The CHI604D electrochemical workstation that adopts Shanghai Chen Hua Instrument Ltd. to produce is surveyed its impedance spectrogram and polarization curve.Obtain by experiment: when the poly(oxyethylene glycol) 400 bridging beta-cyclodextrin concentration that adds example 1 to make is 105mg/L, inhibition efficiency is up to 92.25%.
Claims (2)
1. polyoxyethylene glycol Cyclodextrin Bridged inhibiter, is characterized in that: the chemical name of this Cyclodextrin Bridged inhibiter is polyoxyethylene glycol Cyclodextrin Bridged, and its structural formula is:
In formula, n represents that the polymerization degree of polyoxyethylene glycol is 8-22, symbol
representative ring dextrin is the structural unit of alpha-cylodextrin or beta-cyclodextrin.
2. the preparation method of polyoxyethylene glycol Cyclodextrin Bridged inhibiter as claimed in claim 1, it is characterized in that: first the polyoxyethylene glycol of 0.015-0.02mol is dissolved in the dimethyl sulfoxide solvent of 0-50ml, be placed in dry there-necked flask, under agitation condition, drip the sulfur oxychloride of 0.03-0.04mol, it is-10 ℃ that ice-water bath is controlled temperature of reaction, the temperature that drips reactor in sulfur oxychloride process remains on-10 ℃-0 ℃, and reflux time is 7h; The faint yellow mixed solution of gained is placed on to the Rotary Evaporators distillation 48h in ventilating kitchen, removes the sour gas such as byproduct of reaction hydrogen sulfide and hydrochloric acid, make chloro polyoxyethylene glycol; The chloro the polyoxyethylene glycol again upper step of 0.015-0.02mol being made and 0.03-0.04mol cyclodextrin are placed in ultrasonic stirrer and fully stir 20min, reaction mixture is joined in the reactor that is connected with exhaust gas processing device, question response temperature adds the sodium hydroxide of reactant total mass 7-8% and the Sodium dodecylbenzene sulfonate of 0.2-0.3% to make catalyzer while being increased to 50 ℃ again; After finally above-mentioned solution being mixed, inflated with nitrogen 20min removes oxygen, and controlling temperature of reaction is 60 ℃, and the stirring reaction time is 7-8h, pours gained brown color mixed solution in beaker standing cooling 1h, with dilute hydrochloric acid, the solution obtaining is neutralized to pH=7; Decompress filter is removed unreacted cyclodextrin, then gained filtrate is washed 3-5 time with dehydrated alcohol, finally, gained solid dry 24h in the baking oven of 30 ℃, makes white solid powder polyoxyethylene glycol Cyclodextrin Bridged.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222674A (en) * | 2016-08-08 | 2016-12-14 | 贵州大学 | A kind of melon compound hydrochloric acid pickling corrosion inhibitor of ring class |
| CN108936095A (en) * | 2018-09-11 | 2018-12-07 | 安徽涂远农业有限公司 | A kind of cray special feed and cultural method maintaining water quality |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
| CN111812258A (en) * | 2020-07-23 | 2020-10-23 | 福州大学 | Preparation method and application of polar bridged cyclodextrin chiral monolithic column |
| CN117264497A (en) * | 2022-09-29 | 2023-12-22 | 何舟涛 | Corrosion-resistant coating method for complex nodes of ocean platform |
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2013
- 2013-11-12 CN CN201310562650.0A patent/CN103556158B/en not_active Expired - Fee Related
Patent Citations (4)
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| JPH0748451A (en) * | 1993-08-05 | 1995-02-21 | Nippon Shokuhin Kako Co Ltd | Cyclodextrin polymer and production thereof |
| CN1294204A (en) * | 1999-11-02 | 2001-05-09 | 沈林华 | Multifunctional treating liquid for surface of iron or steel |
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| Title |
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| YASUSHI HASEGAWA，ET.AL: "Supramolecular Polymers Formed from β-Cyclodextrins Dimer Linked by Poly(ethylene glycol) and Guest Dimers", 《MACROMOLECULES》, vol. 38, no. 9, 25 March 2005 (2005-03-25), pages 3725 - 3726 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222674A (en) * | 2016-08-08 | 2016-12-14 | 贵州大学 | A kind of melon compound hydrochloric acid pickling corrosion inhibitor of ring class |
| CN106222674B (en) * | 2016-08-08 | 2018-12-07 | 贵州大学 | A kind of compound hydrochloric acid pickling corrosion inhibitor of melon ring class |
| CN108936095A (en) * | 2018-09-11 | 2018-12-07 | 安徽涂远农业有限公司 | A kind of cray special feed and cultural method maintaining water quality |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
| CN111812258A (en) * | 2020-07-23 | 2020-10-23 | 福州大学 | Preparation method and application of polar bridged cyclodextrin chiral monolithic column |
| CN117264497A (en) * | 2022-09-29 | 2023-12-22 | 何舟涛 | Corrosion-resistant coating method for complex nodes of ocean platform |
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