CN104404525A - Method and special-purpose preparation for preventing oil gas pipeline and equipment from being corroded - Google Patents
Method and special-purpose preparation for preventing oil gas pipeline and equipment from being corroded Download PDFInfo
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- CN104404525A CN104404525A CN201410645990.4A CN201410645990A CN104404525A CN 104404525 A CN104404525 A CN 104404525A CN 201410645990 A CN201410645990 A CN 201410645990A CN 104404525 A CN104404525 A CN 104404525A
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Abstract
The invention discloses a special-purpose preparation for preventing an oil gas pipeline and equipment from being corroded and a method of using the special-purpose preparation to prevent the oil gas pipeline and equipment from being corroded, and influences caused by pH stabilizing agent concentration, glycol concentration and pH value variation are fully given consideration. The special-purpose preparation is composed of a pH stabilizing agent aqueous solution with the mass fraction of 30%-70% and a glycol aqueous solution with the volume fraction of 65%-85%, and the volume ratio of the pH stabilizing agent aqueous solution to the glycol aqueous solution is 1:(13-17). The special-purpose preparation has relatively good compatibility and corrosion inhibition performance, is widely applicable to corrosion protection for CO2-containing natural gas field well mouth and seabed pipelines, and provides an effective means for controlling corrosion.
Description
Technical field
The invention belongs to gas pipeline and equipment corrosion protection field, being specifically related to a kind of for containing CO
2the method of natural gas field well head and subsea pipeline and equipment corrosion protection and special preparation thereof.
Background technology
In the performance history of natural gas field, CO
2corrosion is one of main form of corrosion of running into of gas pipeline and equipment.The Sweet natural gas of the humidity in pipeline, runs into colder tube wall, condensation can go out water of condensation, the CO be mixed in thus moist Sweet natural gas
2can reduce the pH value of condensation water, be the important factor accelerating pipeline corrosion.Current deep-water subsea line of pipes still mainly adopts carbon steel as piping material.For ensureing the service life of pipeline, pH stablizer can be used as control CO
2one of main alleviation means of corrosion.In pipeline, add alkaline matter, be salt by volatile acid neutralization in pipeline, effectively can reduce the dividing potential drop of sour gas in saturated vapor pressure, improve the pH value of condensation water, alleviate and reduce the risk that corrosion occurs pipeline.Current pH stablizer can be divided into organic bases and mineral alkali, and conventional organic bases is N methyldiethanol amine (MDEA), and conventional mineral alkali mainly contains NaOH and NaHCO
3deng.Mineral alkali as the advantage that pH stablizer is maximum be with low cost, the feature of environmental protection good, filling is convenient, also reusable edible.
Ethylene glycol (MEG) has the effect suppressing gas hydrate formation in submerged pipeline, prevent Sweet natural gas under high pressure, low temperature and free-water existent condition, hydrocarbon component and water molecules may in conjunction with the white water compound xln forming ice and snow shape, stick on tube wall, obstruction is caused to e-quipment and pipe.
At present, for MEG and pH stablizer composite and composite after performance lack research, particularly MEG and pH stablizer is at the scene in use procedure, need the pH regulator ability after taking into full account MEG and pH compound stabilizer and compatibility etc., can better play its regulating effect after making MEG and pH compound stabilizer, therefore this aspect needs further investigation further.
Summary of the invention
The object of this invention is to provide a kind of method and the special preparation thereof that prevent gas pipeline and equipment corrosion, for controlling containing CO
2the etching problem of natural gas field well head and subsea pipeline and equipment.
A kind of special preparation protected for gas pipeline and equipment corrosion provided by the present invention, be made up of the pH stablizer aqueous solution and aqueous glycol solution, wherein, the massfraction of the described pH stablizer aqueous solution is 30% ~ 70%, the volume fraction of described aqueous glycol solution is 65% ~ 85%, and the volume ratio of the described pH stablizer aqueous solution and aqueous glycol solution is 1:(13 ~ 17).
In above-mentioned special preparation, described pH stablizer is selected from organic bases and/or mineral alkali, is specifically selected from following at least one: sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide and N methyldiethanol amine (MDEA).
In the described pH stablizer aqueous solution, the massfraction of pH stablizer is 50%-70%.
In described aqueous glycol solution, the volume fraction of ethylene glycol is 70% ~ 80%, is preferably 75%.
The present invention adopts described special preparation to prevent the method for gas pipeline and equipment corrosion, is be added into by special preparation in ethylene glycol filling apparatus, is filled into continuously in gas pipeline to be protected and equipment, and with pH to 6.5 ~ 8.0 of buffered soln regulation system.
In aforesaid method, described buffered soln is phosphate buffer soln, Na
2cO
3with NaHCO
3the buffered soln etc. of composition.
The compound method of described phosphate buffer soln (pH=5.8) is as follows: get potassium primary phosphate 8.34g and dipotassium hydrogen phosphate 0.87g, add water and make it be dissolved into 1000ml, to obtain final product.
The compound method of described phosphate buffer soln (pH=7.8 ~ 8.0) is as follows: get dipotassium hydrogen phosphate 5.59g and potassium primary phosphate 0.41g, add water and make it be dissolved into 1000ml, to obtain final product.
Described ethylene glycol filling apparatus is conventional for ethylene glycol to be filled into the device in pipeline as deicing fluid on oil-gas field.
The material of described gas pipeline and equipment is carbon steel material.
The special preparation protected for gas pipeline and equipment corrosion provided by the present invention, take into full account the impact that MEG concentration and pH value change, this special preparation has better pH regulator ability and compatibility, can be widely applied to containing CO
2in the corrosion prevention of natural gas field well head and subsea pipeline, it is the effective means of control corrosion rate.
Embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
One, compound property in the simulated formation aqueous solution of the pH stablizer aqueous solution and aqueous glycol solution and fouling tendency experiment:
Test medium: base fluid used is the simulated formation aqueous solution, preparation simulated formation aqueous solution agents useful for same is analytical pure, and the composition of simulated formation water is shown in Table 1.
The component list of table 1 simulated formation water
| Medicine | CaCl 2 | NaCl | KNO 3 | MgCl 2 | BaCl 2 | NaNO 3 |
| Concentration (mg/L) | 1148.9 | 2743.7 | 877.8 | 578.4 | 25.6 | 1533.2 |
Reference examples 1: preparation massfraction is the aqueous sodium hydroxide solution of 30%, stirs, is cooled to room temperature.Then get the aqueous sodium hydroxide solution of 5ml prepared 30%, join in the simulated formation water of 95ml.
Reference examples 2: preparation massfraction is the sodium bicarbonate aqueous solution of 70%, stirs, is cooled to room temperature.Then get the sodium bicarbonate aqueous solution of 5ml prepared 70%, join in the simulated formation water of 95ml.
Reference examples 3: preparation massfraction is the MDEA aqueous solution of 30%, stirs, is cooled to room temperature.Then get the MDEA aqueous solution of 5ml prepared 30%, join in the simulated formation water of 95ml.
Reference examples 4: preparation massfraction is the aqueous sodium hydroxide solution of 30%, stirs, is cooled to room temperature.Then get the aqueous sodium hydroxide solution of 15ml prepared 30%, join in the simulated formation water of 85ml.
Reference examples 5: preparation massfraction is the sodium bicarbonate aqueous solution of 70%, stirs, is cooled to room temperature.Then get the sodium bicarbonate aqueous solution of 15ml prepared 70%, join in the simulated formation water of 85ml.
Reference examples 6: preparation massfraction is the MDEA aqueous solution of 30%, stirs, is cooled to room temperature.Then get the MDEA aqueous solution of 15ml prepared 30%, join in the simulated formation water of 85ml.
Embodiment 7: preparation massfraction is the aqueous sodium hydroxide solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 85% again, is finally joined in the simulated formation aqueous solution of the 10ml prepared according to table 1 by the MEG aqueous solution of 85ml, then adds 5ml aqueous sodium hydroxide solution wherein.
Embodiment 8: preparation massfraction is the sodium bicarbonate aqueous solution of 70%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 85% again, is finally joined in the simulated formation aqueous solution of the 10ml prepared according to table 1 by the MEG aqueous solution of 85ml, then adds 5ml sodium bicarbonate aqueous solution wherein.
Embodiment 9: preparation massfraction is N methyldiethanol amine (MDEA) aqueous solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 85% again, is finally joined in the simulated formation aqueous solution of the 10ml prepared according to table 1 by the MEG aqueous solution of 85ml, then adds the 5ml MDEA aqueous solution wherein.
Embodiment 10: preparation massfraction is the aqueous sodium hydroxide solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 75% again, is finally joined in the simulated formation aqueous solution of the 20ml prepared according to table 1 by the MEG aqueous solution of 75ml, then adds 5ml aqueous sodium hydroxide solution wherein.
Embodiment 11: preparation massfraction is the sodium bicarbonate aqueous solution of 70%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 75% again, is finally joined in the simulated formation aqueous solution of the 20ml prepared according to table 1 by the MEG aqueous solution of 75ml, then adds 5ml sodium bicarbonate aqueous solution wherein.
Embodiment 12: preparation massfraction is the MDEA aqueous solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 75% again, is finally joined in the simulated formation aqueous solution of the 20ml prepared according to table 1 by the MEG aqueous solution of 75ml, then adds the 5ml MDEA aqueous solution wherein.
Embodiment 13: preparation massfraction is the aqueous sodium hydroxide solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 65% again, is finally joined in the simulated formation aqueous solution of the 30ml prepared according to table 1 by the MEG aqueous solution of 65ml, then adds 5ml aqueous sodium hydroxide solution wherein.
Embodiment 14: preparation massfraction is the sodium bicarbonate aqueous solution of 70%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 65% again, is finally joined in the simulated formation aqueous solution of the 30ml prepared according to table 1 by the MEG aqueous solution of 65ml, then adds 5ml sodium bicarbonate aqueous solution wherein.
Embodiment 15: preparation massfraction is the MDEA aqueous solution of 30%, stirs, is cooled to room temperature.Dose volume mark is the MEG aqueous solution of 65% again, is finally joined in the simulated formation aqueous solution of the 30ml prepared according to table 1 by the MEG aqueous solution of 65ml, then adds the 5ml MDEA aqueous solution wherein.
Experimental data and conclusion: test instrument and equipment are the portable pH meter of METTLER TOLEDO FG2-, the test effect that compound property in the simulated formation aqueous solution of the pH stablizer aqueous solution in embodiment 1 ~ 15 and aqueous glycol solution and fouling tendency are tested is as shown in table 2.
Table 2
Can be observed from above-mentioned table 2: after only adding the pH stablizer aqueous solution embodiment 1 ~ 6, (adjustment of pH value is by conventional buffered soln to adjust ph in any case, as phosphate buffer soln etc. regulates), all there is turbid phenomenon in system, have floss to precipitate and generate, but when not only having added the pH stablizer aqueous solution but also added aqueous glycol solution in embodiment 7 ~ 15, by adjust ph in 6.5 ~ 8.0 scopes, finally can obtain without flocculent precipitate and the clarification system without fouling tendency, as: in embodiment 7 ~ 12, when pH value reaches 8.0, system is without flocculent precipitate and the clarification system without fouling tendency, in embodiment 13 ~ 14, when pH value reaches 7.5, system is without flocculent precipitate and the clarification system without fouling tendency, particularly in embodiment 11, be be in 6.5 ~ 8.0 scopes without flocculent precipitate and the clarification system without fouling tendency in pH value.Visible composite by the pH stablizer aqueous solution and aqueous glycol solution, obviously can reduce the fouling tendency of the pH stablizer aqueous solution in the simulated formation aqueous solution, be applied to better containing CO
2in the corrosion prevention of natural gas field well head and subsea pipeline.
For testing its compatibility further, after we add the HYH-9 inhibiter 30ppm on oil field again in embodiment 11, system transparent and homogeneous, without flocculent precipitate occur, compatibleness is good.
2) CO
2corrosion simulated experiment:
High Temperature High Pressure FCZ magnetic force driving reactor is utilized to carry out CO
2corrosion simulated experiment, simulated formation water constituent used is as shown in table 1.
Experiment condition: sample is external diameter 108mm, 1/8 annulus of internal diameter 100mm and face width 11mm (material is X65 steel), and experimental temperature is 53 DEG C, and experimental pressure is 0.1MPa, and rotating speed is 0.2m/s, and abrasion cycle is 72h, and the simulated formation aqueous solution is 3L.
Roughly experimental procedure is: first use waterproof abrasive paper (800#) to polish annulus to its smooth surface, by washed with de-ionized water, dry up after acetone oil removing, lacing film (i.e. annulus) is arranged on fixture, the corrosion simulated solution (i.e. the corrosion simulated aqueous solution) of deoxygenation is added again in reactor, then add aqueous glycol solution and the pH stablizer aqueous solution, with the pH to 7.5 of buffered soln regulation system, continue after sealing to pass into CO
2deoxygenation 2h, to remove the O be mixed in installation process
2.Raised temperature to 53 DEG C, opens CO
2tank valve, makes reacting kettle inner pressure reach 0.1MPa, and then opening electrode setting rotating speed is 0.2m/s.
Reference examples 16: according to described experiment condition and experimental procedure, regulates the pH value to 7.5 of the simulated formation aqueous solution, corrodes and record reacted pH value and erosion rate after 3 days with phosphate buffer soln.
Reference examples 17: according to described experiment condition and experimental procedure, adds the 500mL 75%MEG aqueous solution, by phosphate buffer soln adjust ph to 7.5, corrodes and records reacted pH value and erosion rate after 3 days.
Reference examples 18: according to described experiment condition and experimental procedure, the NaOH aqueous solution adding 5mL 30%, as the pH stablizer aqueous solution, by phosphate buffer soln adjust ph to 7.5, corrodes and records reacted pH value and erosion rate after 3 days.
Reference examples 19: according to described experiment condition and experimental procedure, adds the NaHCO of 5mL 70%
3the aqueous solution, as the pH stablizer aqueous solution, by phosphate buffer soln adjust ph to 7.5, corrodes and records reacted pH value and erosion rate after 3 days.
Reference examples 20: according to described experiment condition and experimental procedure, the MDEA aqueous solution adding 5mL 30%, as the pH stablizer aqueous solution, by phosphate buffer soln adjust ph to 7.5, corrodes and records reacted pH value and erosion rate after 3 days.
Embodiment 21: according to described experiment condition and experimental procedure, add the NaOH aqueous solution of 5mL 30% as the pH stablizer aqueous solution, add the 500mL 75%MEG aqueous solution again, by phosphate buffer soln adjust ph to 7.5, corrode and record reacted pH value and erosion rate after 3 days.
Embodiment 22: according to described experiment condition and experimental procedure, adds the NaHCO of 5mL 70%
3the aqueous solution as the pH stablizer aqueous solution, then adds the 500mL 75%MEG aqueous solution, by phosphate buffer soln adjust ph to 7.5, corrodes and records reacted pH value and erosion rate after 3 days.
Embodiment 23: according to described experiment condition and experimental procedure, add the MDEA aqueous solution of 5mL 30% as the pH stablizer aqueous solution, add the 500mL 75%MEG aqueous solution again, by phosphate buffer soln adjust ph to 7.5, corrode and record reacted pH value and erosion rate after 3 days.
Embodiment 16 ~ 23 is respectively lacing film (i.e. annulus) at the simulated formation aqueous solution, the simulated formation aqueous solution adding pH stablizer or the CO added in the simulated formation aqueous solution of composite pH stablizer and MEG
2corrosion simulated experiment, concrete experimental result is as shown in table 3.Slowly-releasing efficiency in table 3 is obtained by following formulae discovery.
V in formula
0for not adding the rate of metal corrosion when pH stablizer aqueous solution and aqueous glycol solution, mm/a; V is the rate of metal corrosion after adding the pH stablizer aqueous solution and/or aqueous glycol solution, mm/a; η is the inhibition efficiency of inhibiter.
Table 3
Can be observed from above-mentioned table 3, according to the optimum experimental condition that table 2 filters out, carried out the CO of high-temperature high-pressure reaction kettle
2corrosion simulated experiment, not adding corrosion of metal speed in the embodiment 16 of pH stablizer and MEG is 3.56mm/a, and after adding pH stablizer and/or MEG, corrosion of metal speed obviously reduces, after particularly adding pH stablizer and MEG simultaneously, comparatively other embodiments, corrosion of metal speed is lower, and slowly-releasing efficiency reaches more than 93%.
Claims (7)
1. the special preparation protected for gas pipeline and equipment corrosion, be made up of the pH stablizer aqueous solution and aqueous glycol solution, wherein, the massfraction of the described pH stablizer aqueous solution is 30% ~ 70%, the volume fraction of described aqueous glycol solution is 65% ~ 85%, and the volume ratio of the described pH stablizer aqueous solution and aqueous glycol solution is 1:(13 ~ 17).
2. special preparation according to claim 1, is characterized in that: described pH stablizer is selected from organic bases and/or mineral alkali.
3. special preparation according to claim 1 and 2, is characterized in that: described pH stablizer is selected from following at least one: sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide and N methyldiethanol amine.
4. the special preparation according to any one of claim 1-3, is characterized in that: in the described pH stablizer aqueous solution, the massfraction of pH stablizer is 40% ~ 60%;
Described ethylene glycol exists with the form of aqueous glycol solution, and in described aqueous glycol solution, the volume fraction of ethylene glycol is 70% ~ 80%.
5. prevent the method for gas pipeline and equipment corrosion, that the special preparation being used for gas pipeline and equipment corrosion protection according to any one of claim 1-4 is added in ethylene glycol filling apparatus, be filled into continuously in gas pipeline to be protected and equipment, and with pH to 6.5 ~ 8.0 of buffered soln regulation system.
6. method according to claim 5, is characterized in that: described buffered soln is phosphate buffer soln or sodium carbonate-bicarbonate buffered soln.
7. the method according to claim 5 or 6, is characterized in that: the material of described gas pipeline and equipment is carbon steel material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104898724A (en) * | 2015-06-10 | 2015-09-09 | 中国石油天然气集团公司 | Automatic pH value control device for sulfide stress cracking resistance test, and control method thereof |
| CN115477930A (en) * | 2021-05-31 | 2022-12-16 | 中国石油天然气集团有限公司 | PH stabilizer for drilling fluid and application method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104898724A (en) * | 2015-06-10 | 2015-09-09 | 中国石油天然气集团公司 | Automatic pH value control device for sulfide stress cracking resistance test, and control method thereof |
| CN104898724B (en) * | 2015-06-10 | 2017-02-22 | 中国石油天然气集团公司 | Automatic pH value control device for sulfide stress cracking resistance test, and control method thereof |
| CN115477930A (en) * | 2021-05-31 | 2022-12-16 | 中国石油天然气集团有限公司 | PH stabilizer for drilling fluid and application method thereof |
| CN115477930B (en) * | 2021-05-31 | 2023-06-30 | 中国石油天然气集团有限公司 | PH stabilizer for drilling fluid and application method thereof |
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Application publication date: 20150311 |