CN102061157A - Gas-liquid double-phase corrosion inhibitor for gas well and preparation method thereof - Google Patents
Gas-liquid double-phase corrosion inhibitor for gas well and preparation method thereof Download PDFInfo
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Abstract
The invention provides a gas-liquid double-phase corrosion inhibitor for a gas well and a preparation method thereof, relating to the technical field of petrochemical industry. The corrosion inhibitor comprises the following components in percentage by weight: 10-20 percent of naphthenic imidazoline, 10-20 percent of alkynol, 20-30 percent of nonionic surfactant and 30-60 percent of solvent. The corrosion inhibitor can be used for solving the problem of difficult inhibition to corrosion of the upper part of a shaft, corrosion inside a gas pipeline, and the like of the traditional liquid-phase corrosion inhibitor. The corrosion inhibitor has the characteristics of less dosage, long drug effect, no pollution, no damage to human bodies, and the like, can be used for effectively controlling corrosion when applied to actual production and can save the production cost and achieve the purposes of reducing the cost and increasing the efficacy.
Description
Technical field
The present invention relates to the petrochemical technology field, exactly relate to a kind of gas well pit shaft, inner gas-liquid two-phase corrosive gas-liquid two-phase inhibiter that occurs of gas transmission line and preparation method thereof of suppressing.
Background technology
Along with greatly developing of oil-gas field, the exploitation of Sweet natural gas continues deeply to carry out, and contains H
2S, CO
2, Cl
-And the oil-gas field of multiple corrosive medium such as hydrate occurs in succession, and flow string, sleeve pipe, surface pipeline also expose serious tubing string, pipeline corrosion, perforation or the fracture problem that hole conditions such as well worsen that falls simultaneously.External in recent years accident analysis and research tendency show that the corrosion of oil-gas field mainly is H
2S and CO
2Corrosion, wherein the gas-liquid two-phase etching problem in pit shaft and the pipeline becomes the focus of Recent study.
In gas well, increase along with condensation water quantity, liquid water can tend to flow on one side along hole deviation, so in the flowing water bottom corrosive medium can be dissolved on the one hand the bottom of pipeline is corroded, the liquid film that also can be dissolved in tube wall on the other hand corrodes all the other positions of pipeline, and produces the corrosion of gas-liquid two-phase.
Along with the increasing of pipeline, gas transmission distance and the increase of working life, the accident that internal corrosion causes constantly increases.Therefore, internal corrosion control is to reduce pipeline accident, guarantees to produce the important measures of normal operation.The generation of internal corrosion also with CO
2, H
2S exists relevant with water, under certain condition, as the desert area day and night temperature, making daytime in the Sweet natural gas is that the water that the water vapour form exists forms moisture film to the internal surface that can condense in pipe night, hydrogen sulfide and carbonic acid gas dissolving also very easily reach the pipe face, make metal generation hydrogen evolution corrosion, produce gaseous corrosion; The high-moisture Sweet natural gas is separated out water after temperature reduces, rest on the low-lying place of pipeline, causes the corrosion of stronger water-line corrosion and liquid phase.
Pacify the border region and contain CO in the Sweet natural gas of gas field in long celebrating oil field
2And H
2S, content is slightly different with the block different distributions, and average content is respectively: 4.6% and 824mg/L.Stratum product water feature is obvious, and output water is mainly condensation water, and water type major part is CaCl
2The water type, average salinity 41.29g/L.Lip river river layer about 1200 meters and about 2400 meters long 4+5 layer are " severely afflicated areas " that corrosion phenomenon takes place because water temperature is lower, and water vapour easily condenses at this.Though most of gas well taked the well cementation of full well section respectively, use anti-sulphur pipe, galvanic protection and add safeguard procedures such as inhibiter, produces little effect, etching problem is still perplexing the normal activity in gas field.
At the unripe supporting aseptic technic of at present serious day by day gas-liquid two-phase corrosion; main sfgd. comprises: change corrosion-resistant material, coating and filling inhibiter; as publication number is CN1778994; the Chinese patent literature that open day was on May 31st, 2006 discloses a kind of polyaniline oil well inhibiter, it is characterized in that being made up of the component of following weight percent: polyaniline aqueous sanitas 20～30% amine hydroxybenzene 20～30% diethanolamine, 20～30% urea 20～30% but have following problem:
1, integral replacing corrosion resistant alloy material cost height, local replacing easily forms potential difference, accelerated corrosion;
2, existing inhibiter can only can not satisfy the corrosive medium of gas-liquid two-phase coexistence at single gas phase or liquid phase corrosive medium;
3, existing inhibiter consumption is big, and inhibition efficiency is low;
4, existing inhibiter poor high temperature stability, the corrosion inhibition temperature influence is bigger.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of gas well gas-liquid two-phase inhibiter, the invention solves the technical problems such as upper wellbore burn into gas pipeline internal corrosion that traditional liquid phase inhibiter is difficult to suppress, and inhibition efficiency height, has stronger high thermal resistance, complete processing is simple, especially is suitable for the corrosive medium of gas-liquid two-phase coexistence.
The present invention also provides the preparation method of above-mentioned gas-liquid two-phase inhibiter simultaneously.
The present invention realizes by adopting following technical proposals:
A kind of gas well gas-liquid two-phase inhibiter, it is characterized in that: component comprises by weight percentage:
Cycloalkyl tetrahydroglyoxaline 10%～20%;
Alkynol 10%～20%;
Nonionogenic tenside 20%～30%;
Solvent 30%～60%;
Wherein: described alkynol is C
3～C
6A kind of in the alkynol, described solvent is a kind of in water, methyl alcohol and the ethanol, the general structure of described cycloalkyl tetrahydroglyoxaline is:
N?—?CH
2
∥ ︱
R—C—N—CH
2
︱
R
1
Wherein, R is C
12～C
20Alkyl, R
1Be the organic amine alkyl.
Described cycloalkyl tetrahydroglyoxaline is synthetic by following method: according to weight ratio with the azeotropic agent of 53% naphthenic acid, 30% tetraethylene pentamine and 10% join simultaneously have stir and the reactor of water distilling apparatus in, after reacting 3 hours under 145 ℃～175 ℃, in reactor, drip remaining 7% tetraethylene pentamine again, continue to heat up, reacted 2.5-3 hour down at 240 ℃～260 ℃, obtain the cycloalkyl tetrahydroglyoxaline.
The said water solvent of taking is meant toluene or dimethylbenzene.
Described alkynol is butynol or propiolic alcohol.
Described nonionogenic tenside is Soxylat A 25-7, polyoxyethylene amine, sorbitan monostearate (Span80).
Prepare the method for gas well: it is characterized in that with the gas-liquid two-phase inhibiter: with cycloalkyl tetrahydroglyoxaline, alkynol, nonionogenic tenside and solvent according to described part by weight stir, mixed gas-liquid two-phase corrosion inhibitor product.
Compared with prior art, the beneficial effect that the present invention reached is as follows:
One, among the present invention, adopt the cycloalkyl tetrahydroglyoxaline, alkynol, the well gas-liquid two-phase inhibiter of nonionogenic tenside and solvent preparation, through experiment (concrete experimentation and result are with reference to embodiment) as can be known: the present invention is a water soluble rust inhibitor, utilize the molecular designing method to adopt macromolecular cpd mutually composite with the negatively charged ion of micromolecular compound and specific adsorption, no matter clean or all there is stronger corrosion inhibition the metallic surface that is coated with corrosion products film, can also contain N compound and quaternary ammonium salt etc. with other and unite use, can further improve erosion-resisting ability, improve corrosion inhibition rate greatly, solved the upper wellbore corrosion that traditional liquid phase inhibiter is difficult to suppress, technical problems such as gas pipeline internal corrosion, and inhibition efficiency height, has stronger high thermal resistance, complete processing is simple, especially is suitable for the corrosive medium of gas-liquid two-phase coexistence.
Two, corrosion inhibitor product of the present invention is a kind of water miscible chemical agent, and when adding dose and reaching 200mg/L, erosion rate is less than industry standard value 0.076mm/a.This inhibiter has that consumption is few, drug effect long, pollution-free and can not damage to human body, accepted by the oil field field staff easily.Be applied in the actual production and not only can effectively control corrosion, and can reduce the remedial operation frequency greatly, reach the purpose of cost efficiency.
Three, among the present invention, alkynol is butynol or propiolic alcohol, and solvent adopts water or ethanol better effects if.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but following example only is the present invention's example wherein, the rights protection scope of not representing the present invention and being limited, the scope of the present invention is as the criterion with claims.
Embodiment 1
The invention discloses a kind of gas well gas-liquid two-phase inhibiter, component comprises by weight percentage:
Cycloalkyl tetrahydroglyoxaline 10%～20%;
Alkynol 10%～20%;
Nonionogenic tenside 20%～30%;
Solvent 30%～60%;
Wherein: described alkynol is C
3～C
6A kind of in the alkynol, described solvent is a kind of in water, methyl alcohol and the ethanol, the general structure of described cycloalkyl tetrahydroglyoxaline is:
N?—?CH
2
∥ ︱
R—C—N—CH
2
︱
R
1
Wherein, R is C
12～C
20Alkyl, R
1Be the organic amine alkyl.
The corrosion inhibition of tetrahydroglyoxaline mainly is that the lone-pair electron of nitrogen-atoms and the unoccupied orbital of metal ion form coordinate bond and produce adsorption; oil loving chain alkyl aligns in the metallic surface; form the hydrophobic protective membrane of one deck; cut off the route of exposure of corrosive medium and metal; thereby reached the purpose of mitigate corrosion; stable performance, good heat resistance, applied range.Tetrahydroglyoxaline and derivative thereof are efficient organic inhibitors, are used widely in matting, metal rust preventing; Can be used for the anticorrosion of simultaneous oil gas well of hydrogen sulfide, carbonic acid gas and water and pipeline.
The characteristics of cycloalkyl tetrahydroglyoxaline are the metallic surface excellent adsorption, and spatial disposition is neat, can form in the metallic surface than general inhibiter compact protective film more, suppress corrosive and carry out.The non-polar group majority is arranged in the metallic surface on the other hand, forms hydrophobic membrane, has stoped most of electric charge or the corrosive medium relevant with corrosion reaction to move, and reaches to suppress the corrosive purpose.
Described cycloalkyl tetrahydroglyoxaline is synthetic by following method: according to weight ratio 53% naphthenic acid, 30% tetraethylene pentamine and 10% are taken water solvent and join simultaneously in the reactor that has stirring and water distilling apparatus, after reacting 3 hours under 145 ℃～175 ℃, in reactor, drip the tetraethylene pentamine of residue 7% again, continue to heat up, reacted 2.5-3 hour down at 240 ℃～260 ℃, obtain the cycloalkyl tetrahydroglyoxaline.
Described alkynol and cycloalkyl tetrahydroglyoxaline have the inhibition synergy, can significantly improve the corrosion inhibition of inhibiter, and described alkynol is C
3～C
6A kind of in the alkynol, a kind of in preferred propiolic alcohol and the butynol.
Described nonionogenic tenside is Soxylat A 25-7, polyoxyethylene amine, sorbitan monostearate (Span80).
Described solvent is a kind of in water, methyl alcohol, the ethanol, and is a kind of in preferably water, the ethanol.
The present invention also provides a kind of compound method of described inhibiter, and this method comprises: the above-mentioned synthetic cycloalkyl tetrahydroglyoxaline that obtains is mixed, stirs by proportioning with alkynol, nonionogenic tenside and solvent can obtain above-mentioned gas-liquid two-phase corrosion inhibitor product.Quality product reaches following technical indicator, sees Table 1:
Table 1 technical target of the product
Embodiment 2
The ethanol of 10g cycloalkyl tetrahydroglyoxaline, 10g propiolic alcohol, 20gSpan80 and 60g is mixed mutually, evenly stir the complete water miscible gas-liquid two-phase inhibiter of system.
Embodiment 3
The ethanol of 10g cycloalkyl tetrahydroglyoxaline, 20g propiolic alcohol, 20gSpan80 and 50g is mixed mutually, evenly stir, make complete water miscible gas-liquid two-phase inhibiter.
Embodiment 4
The evaluation of inhibiter: the invention provides the inhibiter corrosion mitigating effect in gas phase and liquid phase respectively in order to verify, the present invention is according to oil and gas industry standard SY/T5273-2000 " oil field extracted water inhibiter method of evaluating performance ", the simulated field corrosive environment adopts weight-loss method that the corrosion mitigating effect of inhibiter is estimated.
Test conditions: (specification: 40mm * 13mm * 2mm) is placed on the gas, liquid in the reagent bottle respectively, reagent bottle is put into 90 ℃ of baking ovens again and is left standstill 48 hours with the N80 steel test piece handled well.
Take out after the off-test, test piece is handled, is weighed by the GB6384-86 method, calculates the erosion rate of test piece by following formula
V, promptly
V=8.76×10
7×(W
1－W
2)/Atρ
In the formula:
V-test piece erosion rate (mm/a); A-test piece area (cm
2); T-test period (h); Density (the 7.8g/cm of ρ-carbon steel
3); W
1-test piece original weight (g); W
2-remove the weight (g) of test piece behind the corrosion product.
Calculate the corrosion inhibition rate E of inhibiter by following formula again, promptly to steel
E=(1－V/V
0)×100%
In the formula: the corrosion inhibition rate of E-inhibiter (%); The erosion rate of test piece behind V-adding inhibiter
(mm/a); V
0The erosion rate of-blank test piece (mm/a).
Table 2 has provided the evaluation result of this inhibiter in 90 ℃ corrosive medium under the different concns.
The evaluation result of table 2 inhibiter in gas phase and liquid phase corrosive medium
Test-results: see from last table, for embodiment in, under above-mentioned test conditions, along with the increase of inhibiter add-on, inhibition efficiency raises, erosion rate reduces.When the inhibiter add-on reached 200mg/L, vapor phase corrosion inhibitor efficient was greater than 90%, and the liquid phase erosion rate is 0.062mm/a, and Corrosion rate in Carbon Steel is all less than industry standard value 0.076mm/a.
Embodiment 5
The composition of evaluation method and inhibiter is with embodiment 3, and estimating inhibiter is 200mg/L in concentration, and temperature is 90 ℃, the corrosion situation in the different pH environment, and Corrosion rate in Carbon Steel is as shown in table 3.
Table 3 pH value is to the corrosion inhibition influence of inhibiter
Test-results: see from last table, for embodiment in, under above-mentioned test conditions, this patent inhibiter is less to the influence of the soda acid character of oil-field water, oil-field water pH under 6～8 conditions Corrosion rate in Carbon Steel all less than industry standard value 0.076mm/a.
In sum, corrosion inhibitor product of the present invention is a kind of water miscible chemical agent, and when adding dose and reaching 200mg/L, erosion rate is less than industry standard value 0.076mm/a.This inhibiter has that consumption is few, drug effect long, pollution-free and can not damage to human body, accepted by the oil field field staff easily.Be applied in the actual production and not only can effectively control corrosion, and can reduce the remedial operation frequency greatly, reach the purpose of cost efficiency.
Claims (6)
1. gas well gas-liquid two-phase inhibiter, it is characterized in that: component comprises by weight percentage:
Cycloalkyl tetrahydroglyoxaline 10%～20%;
Alkynol 10%～20%;
Nonionogenic tenside 20%～30%;
Solvent 30%～60%;
Wherein: described alkynol is C
3～C
6A kind of in the alkynol, described solvent is one or more a mixture in water, methyl alcohol and the ethanol, the general structure of described cycloalkyl tetrahydroglyoxaline is:
N?—?CH
2
∥ ︱
R—C—N—CH
2
︱
R
1
Wherein, R is C
12～C
20Alkyl, R
1Be the organic amine alkyl.
2. gas well gas-liquid two-phase inhibiter according to claim 1, it is characterized in that: described cycloalkyl tetrahydroglyoxaline is synthetic by following method: weight ratio is taken water solvent with 53% naphthenic acid, 30% tetraethylene pentamine and 10% join simultaneously in the reactor that has stirring and water distilling apparatus, after reacting 3 hours under 145 ℃～175 ℃, in reactor, drip the tetraethylene pentamine of residue 7% again, continue to heat up, reacted 2.5-3 hour down at 240 ℃～260 ℃, obtain the cycloalkyl tetrahydroglyoxaline.
3. gas well gas-liquid two-phase inhibiter according to claim 2 is characterized in that: the described water solvent of taking is meant toluene or dimethylbenzene.
4. gas well gas-liquid two-phase inhibiter according to claim 1 is characterized in that: described alkynol is butynol or propiolic alcohol.
5. gas well gas-liquid two-phase inhibiter according to claim 1 is characterized in that: described nonionogenic tenside is Soxylat A 25-7, polyoxyethylene amine, sorbitan monostearate (Span80).
6. prepare the method for gas well as claimed in claim 1: it is characterized in that with the gas-liquid two-phase inhibiter: with cycloalkyl tetrahydroglyoxaline, alkynol, nonionogenic tenside and solvent according to described part by weight stir, mixed gas-liquid two-phase corrosion inhibitor product.
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