CN102585796A - Acidizing corrosion inhibitor N-(gamma-methylanthracene) pyridine chloride and preparation method thereof - Google Patents
Acidizing corrosion inhibitor N-(gamma-methylanthracene) pyridine chloride and preparation method thereof Download PDFInfo
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- CN102585796A CN102585796A CN2012100111876A CN201210011187A CN102585796A CN 102585796 A CN102585796 A CN 102585796A CN 2012100111876 A CN2012100111876 A CN 2012100111876A CN 201210011187 A CN201210011187 A CN 201210011187A CN 102585796 A CN102585796 A CN 102585796A
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Abstract
The invention relates to an acidizing corrosion inhibitor N-(gamma-methylanthracene) pyridine chloride and a preparation method thereof. The pyridine chloride is a condensed-ring group containing pyridine quaternary ammonium salt corrosion inhibitor, and the preparation method of the pyridine chloride is reliable, and easy to operate. The preparation method comprises the following steps: preparing an intermediate gamma-chloro-methylanthracene by using a chloromethylation reaction firstly; and then, carrying out quaternarization on the gamma-chloro-methylanthracene and pyridine so as to obtain N-(gamma-methylanthracene) pyridine chloride, wherein the N-(gamma-methylanthracene) pyridine chloride has a synergistic effect with propiolic alcohol. The corrosion inhibitor disclosed by the invention can quickly achieve an adsorption effect on a metal surface, so that the covering rate of corrosion inhibitor molecules on the metal surface is obviously improved, and therefore, the corrosion inhibitor has the advantages of high adsorption speed, high covering rate, good water solubility and low application amount. The corrosion inhibitor disclosed by the invention belongs to an anodic control based mixed corrosion inhibitor, is excellent in corrosion inhibition property, and can provide good protection for downhole tools, pipe strings and ground facilities, and therefore, the corrosion inhibitor is especially suitable to be applied to the acidizing and acid-fracturing yield-increasing operations of oil and gas wells in oil exploitation, and is expected to have large-scale field application and promotion in oil fields.
Description
Technical field
The present invention relates to N-(γ-methyl anthracene) pyridinium chloride and preparation method thereof, belong to the inhibiter utilisation technology in the oil production acid stimulation technology.
Background technology
Acid stimulation operation in the oil production is acid pump to be annotated get into the subterranean oil gas-bearing formation, removes contamination and plugging thing in the hydrocarbon zone, enlarges the process method of dredging the oil gas flow passage and realizing increasing production.Acid solution can be annotated equipment, manifold of ground, shaft column and subsurface tool to surface pump and produce corrosion in getting into the stratum process.The inhibiter that therefore, need in acid solution, add excellent property reduces the corrosion in the operation process.
Inhibiter is to be present in the environment (medium) with proper concn and form, can prevent or slow down greatly the mixture of a kind of chemical substance of corrosive or several kinds of chemical substances.The acidification of oil gas well inhibiter is one type of work additive that is applicable to strong acid media.Strongly-acid media inhibitor commonly used is main (nitrogenous compound occupies very big ratio) with the organic cpds, comprises following several big type: (1) aldehyde, ketone, amine condenses.Using aldehyde, ketone, amine is the synthetic organic compounds containing nitrogen Mannich base that obtains of raw material, and general molecular weight is less, Stability Analysis of Structures, low toxicity, has excellent development and using value as the inhibiter of acidic medium, like patent 02100697.0 disclosed prescription; (2) imidazolidine derivatives.Kind is more, uses extensivelyr, usually is applied in the Working environment of sulfur-bearing, like patent 96104728.3, patent 89108825.3 disclosed prescriptions; (3) assorted polyamines, the mixture that obtains behind the compound interpolation synergistic agent.Like patent 90104787.2 disclosed prescriptions; (4) macromolecular compound.Utilize natural plant to carry out the nitrogen heterocyclic modification, the inhibiter readily biodegradable, the low toxicity that make are like patent 02134350.0 disclosed prescription.
Summary of the invention
The object of the present invention is to provide acidification corrosion inhibitor N-(γ-methyl anthracene) pyridinium chloride; Can produce adsorption fast in the metallic surface; Significantly improve the hiding rare of inhibiter molecule, have inhibition efficiency height, dissolution rate is fast, consumption is low advantage the metallic surface.
Another object of the present invention also is to provide the preparation method of this pyridinium chloride, and this method principle is reliable, easy to operate, is specially adapted to acidification of oil gas well, acid fracturing stimulation work in the oil production, also can adapt to extensive rig-site utilization in oil field and popularization.
Inhibiter of the present invention is a kind of pyridine quaternary ammonium salt inhibiter of novel band condensed ring; Have that rate of adsorption is fast, hiding rare is high, good water solubility, advantage that consumption is low; Belonging to the anodic control is main hybrid corrosion inhibitor; Corrosion inhibition is excellent, can excellent protection be provided for subsurface tool, pipe string and uphole equipment.Its synthetic schemes is comparatively simple with operation, at first utilizes chloromethylation to make midbody γ-chloromethyl anthracene; Carry out quaterisation with γ-chloromethyl anthracene and pyridine again and make N-(γ-methyl anthracene) pyridinium chloride, this pyridine quaternary ammonium salt acidification corrosion inhibitor and propiolic alcohol have synergy.
The present invention is the pyridine quaternary ammonium salt class inhibiter of band condensed ring group, N-(γ-methyl anthracene) pyridinium chloride, and its structural formula is following:
Its preparation method may further comprise the steps successively:
(1) chloromethylation prepares γ-chloromethyl anthracene.At first chloromethylation is taken place in anthracene, Paraformaldehyde 96 and hydrochloric acid under acetic acid catalysis, preparation midbody γ-chloromethyl anthracene.Reaction formula is following:
(2) midbody γ-chloromethyl anthracene separation and purification.After reaction finishes, extract, wash, drying, dried solution is distilled under normal pressure, remove extraction liquid, underpressure distillation then, remaining oily body staple at last is γ-chloromethyl anthracene.
(3) quaterisation prepares N-(γ-methyl anthracene) pyridinium chloride.With separate, behind the purifying midbody γ-chloromethyl anthracene carry out quaterisation with pyridine and synthesize N-(γ-methyl anthracene) pyridinium chloride.Reaction formula is following:
After reaction finishes, add Virahol, be made into the N-that concentration is 60 quality % (γ-methyl anthracene) pyridinium chloride corrosion inhibitor solution, can use at the scene as solvent.This inhibiter and some synergistic agent (like propiolic alcohol) have synergy.
Compared with prior art, the present invention has following outstanding feature: (1) dosage is low, and inhibition efficiency is high.In the acidification of oil field stimulation work, the acidification corrosion inhibitor working concentration is higher at present, common dosage 1.0%-4.0%, and inhibiter dosage of the present invention is merely the requirement that 0.5%-1.0% just can reach oil ministerial standard SY/T 5405-1996; (2) water-soluble extremely strong.Because system of the present invention is a quaternary ammonium salt, its solubility in acid, water-soluble all very strong, some not quaternised mannich base inhibiter solvability in bright acid is fine; After in case acid liquid reaction becomes weary acid; The acid reduction, inhibiter will be separated out from acid, layering, adsorbs in the rock duct.
Description of drawings
Fig. 1 is the polarization curve of inhibiter of the present invention.
Embodiment
The preparation of inhibiter N-(γ-methyl anthracene) pyridinium chloride:
(1) chloromethylation prepares γ-chloromethyl anthracene.Synthetic operation is: in the 500mL of belt stirrer, reflux exchanger and TM there-necked flask, add successively: 50～60g anthracene; 15～20g Paraformaldehyde 96,80mL acetic acid, (phosphoric acid can reduce reaction activity to 20mL phosphoric acid; Increase speed of response); And 50mL hydrochloric acid, under agitation be heated to 95 ℃, backflow 10h;
(2) midbody γ-chloromethyl anthracene separation and purification.After reaction finishes, use 100mL1, the 2-ethylene dichloride extracts, extraction liquid water and 12% K
3PO
4 Solution washing extracts 3～4 times repeatedly, is neutral until water layer, till the no cl ions.Tell the ethylene dichloride liquid layer, add an amount of Calcium Chloride Powder Anhydrous drying.Dried solution is distilled under normal pressure, remove ethylene dichloride, underpressure distillation then boils off the material of boiling point before 180 ℃, and left object is dark brown dark oil body, and its staple is γ-chloromethyl anthracene;
(3) quaterisation prepares N-(γ-methyl anthracene) pyridinium chloride.Synthetic operation is following: in the there-necked flask of belt stirrer, reflux exchanger and TM, add γ-chloromethyl anthracene of 30g, 2～5g pyridine is heated with stirring to 105 ℃, backflow 4h.
Add Virahol after reaction finishes, be made into the N-that concentration is 60 quality % (γ-methyl anthracene) pyridinium chloride corrosion inhibitor solution.
N-(γ-methyl anthracene) pyridinium chloride aqueous isopropanol, 95.0 quality %;
Propiolic alcohol, 5.0 quality %.
The performance test of inhibiter N-(γ-methyl anthracene) pyridinium chloride
The mensuration of the inhibiter sample inhibition efficiency of embodiment 1 and embodiment 2 preparations
Erosion rate is measured with classical weight-loss method.Experimental procedure: 6 of the desired standard N80 steel discs of corrosion test are got in (1), water, ethanol, acetone edulcoration, and cold wind dries up then, puts into moisture eliminator, and record number is also weighed; (2) in the standard reaction bottle, adding 200mL concentration is 20%HCl, puts into thermostatted, at 90 ℃ of following constant temperature 20min.Hang up 2 of the steel discs of the clean dried of known surface area and weight then, at 90 ℃ of reaction 0.5h down.This is a blank assay; (3) get 4 standard reaction bottles in addition, add 200mL concentration 20%HCl respectively, 0.5% inhibiter (inhibiter of embodiment 1 and embodiment 2 preparations, 2 parallel appearance of each sample), the reaction times is 4h; (4) after reaction finishes, water, ethanol, acetone edulcoration successively, cold wind dries up then, puts into moisture eliminator, weighs behind the 5min; (5) corrosion inhibition rate of calculating inhibiter.
Table 1 embodiment 1 measures with embodiment 2 corrosion inhibitor formula slow rates
Visible by table 1; N-(γ-methyl anthracene) pyridinium chloride corrosion inhibitor solution has good corrosion inhibiting effect; Simultaneously, have synergistic effect after N-(γ-methyl anthracene) pyridinium chloride and propiolic alcohol are composite, can further improve the corrosion mitigating effect of N-(γ-methyl anthracene) pyridinium chloride inhibiter.
Embodiment 4
The electro-chemical test of the inhibiter sample of embodiment 1 and embodiment 2 preparations
In the 20%HCl medium, utilize the three-electrode electro Chemical system, test the corrosion electric current density of N80 electrode behind blank medium and interpolation inhibiter respectively.Inlaying N80 Oil Tube Steel lacing film is working electrode, exposed area 1cm
2, use the abrasive paper for metallograph sanding and polishing; Reference electrode is SCE (SCE); Supporting electrode is a platinum electrode.Carry out weak polarization scan with the D1702H potentiostat, electric potential scanning scope ± 250mV, sweep velocity 50mV/min.Data are with weak polarization curve match software processes, the figure of the lgi-E that obtains being correlated with.See Fig. 1 (1-1 ' for 20%HCl blank polarization curve; 2-2 ' is for adding the polarization curve of 0.5% embodiment, 1 inhibiter sample; 3-3 ' is for adding the polarization curve of 0.5% embodiment, 2 inhibiter samples).
With reference to simultaneous test, in the 20%HCl medium, 0.5% embodiment, 1 inhibiter and 0.5% embodiment, 2 inhibiter have reduced the corrosion electric current density of N80 electrode system significantly, make corrosion potential to positive dirction generation minor shifts.In the Ta Feier district; It is big that the slope of anodic polarization curves obviously becomes; More violent than cathodic polarization curve slope variation; Show that this N-(γ-methyl anthracene) pyridinium chloride inhibiter has had strong inhibitory effects to the active dissolution process in metal anode district, greatly reduce the corrosion current of system, belonging to the anodic control is main hybrid corrosion inhibitor.
Claims (2)
1. acidification corrosion inhibitor N-(γ-methyl anthracene) pyridinium chloride, its structural formula is following:
2. the preparation method of pyridinium chloride as claimed in claim 1 may further comprise the steps successively:
(1) chloromethylation is taken place in anthracene, Paraformaldehyde 96 and hydrochloric acid under acetic acid catalysis, preparation midbody γ-chloromethyl anthracene;
(2) with midbody γ-chloromethyl anthracene extract, wash, dry, distillation;
(3) will separate, the midbody γ-chloromethyl anthracene behind the purifying and pyridine carry out quaterisation and obtain N-(γ-methyl anthracene) pyridinium chloride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571451A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 120 to 140 DEG C, and preparation and application thereof |
| CN103571452A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 140 to 160 DEG C, and preparation and application thereof |
| CN104232073A (en) * | 2014-09-10 | 2014-12-24 | 滨州学院 | Preparation method of [1,5] benzodiazepine compound and application of [1,5] benzodiazepine compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382638A (en) * | 2011-09-20 | 2012-03-21 | 南京华洲新材料有限公司 | Application of pyridine compound for preparing acidization corrosion inhibitors |
| CN102499246A (en) * | 2011-09-20 | 2012-06-20 | 南京华洲新材料有限公司 | Application of pyridines compound as bactericide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382638A (en) * | 2011-09-20 | 2012-03-21 | 南京华洲新材料有限公司 | Application of pyridine compound for preparing acidization corrosion inhibitors |
| CN102499246A (en) * | 2011-09-20 | 2012-06-20 | 南京华洲新材料有限公司 | Application of pyridines compound as bactericide |
Non-Patent Citations (2)
| Title |
|---|
| FHC STEWART: "The Preparation of Some Surface Active Alcohols Containing the Anthracene Nucleus", 《AUSTRALIAN JOURNAL OF CHEMISTRY》 * |
| RICHARD A. HANN ET AL: "Inter- and Intra-molecular Quenching of Anthracene Fluorescence by Pyridinium Ion in Solution", 《J. CHEM. SOC., FARADAY TRANS. 2》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571451A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 120 to 140 DEG C, and preparation and application thereof |
| CN103571452A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 140 to 160 DEG C, and preparation and application thereof |
| CN103571451B (en) * | 2012-07-26 | 2016-02-10 | 中国石油天然气集团公司 | One is applicable to 120 DEG C ~ 140 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications |
| CN103571452B (en) * | 2012-07-26 | 2016-02-10 | 中国石油天然气集团公司 | One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof |
| CN104232073A (en) * | 2014-09-10 | 2014-12-24 | 滨州学院 | Preparation method of [1,5] benzodiazepine compound and application of [1,5] benzodiazepine compound |
| CN104232073B (en) * | 2014-09-10 | 2017-01-18 | 滨州学院 | Preparation method of [1,5] benzodiazepine compound and application of [1,5] benzodiazepine compound |
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