CN103937477A - Controlled-release solid corrosion inhibitor capable of solving underground corrosion of oil well and preparation method thereof - Google Patents
Controlled-release solid corrosion inhibitor capable of solving underground corrosion of oil well and preparation method thereof Download PDFInfo
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- CN103937477A CN103937477A CN201410177728.1A CN201410177728A CN103937477A CN 103937477 A CN103937477 A CN 103937477A CN 201410177728 A CN201410177728 A CN 201410177728A CN 103937477 A CN103937477 A CN 103937477A
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- inhibiter
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
- E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing, limiting or eliminating the deposition of paraffins or like substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention relates to a controlled-release solid corrosion inhibitor capable of solving underground corrosion of an oil well and a preparation method thereof. The controlled release solid corrosion inhibitor capsule is composed of a carrier (namely calcium alginate with developed pore passages), a weighting agent which exists in the pore passages of the carrier and accounts for 10-65% of the total mass percent of the capsule and a solid corrosion inhibitor which exists in the pore passages of the carrier and accounts for 20-80% of the total mass percent of the capsule, wherein the weighting agent adopts BaSO4, ferrotitanium powder, spathic iron powder, CaCO3 or zinc powder, iron powder and other metal powders; the corrosion inhibitor is the conventional liquid corrosion inhibitor for an oil filed, and the liquid corrosion inhibitor is solidified after being made into the capsule. When the prepared solid corrosion inhibitor capsule is put into the oil well, settling property of the capsule is good, and the capsule gradually release the corrosion inhibitor in a swelling and shattering process, so that settling and controlled release of the corrosion inhibitor are realized, and protection effect of the corrosion inhibitor on underground facilities for the oil well is effectively enhanced.
Description
technical field:
The invention belongs to metal corrosion and protection field, relate to the anticorrosion high-temp solid inhibiter of using with inhibiter, particularly oil pipe and sleeve pipe high-temperature anticorrosion of a kind of oil well; The invention still further relates in addition the preparation method of inhibiter.
background technology:
Greenhouse gases CO
2make global warming, the mankind's existence and socioeconomic development have been formed to serious threat.CO
2the efficient manner of geological disposal inject exactly oil-gas field, not only seal CO up for safekeeping
2, also can improve the recovery ratio of oil-gas field.Yet along with CO
2drive the carrying out of oil recovery, CO
2corrosion becomes thorny problem.Be dissolved in and help the CO adopting in solution
2easily form carbonic acid, and ionize out hydrogen ion, thereby cause CO
2" acid corrosion ".Solve this etching problem and mainly contain three kinds of approach: 1. adopt the protection of sacrificial anode method, deep well anode is connected on the carbon steel pipe of oil well, the method can play a very good protection to the dark above tubing and casing of 150 m.Because oil well depth has two or three km, anode is installed at deep-well place will affect oil recovery, so galvanic anode protection maintaining method cannot be applicable to deep-well.2. when underground equipment corrosion occurs cannot use, conventionally adopt the method for changing material, this not only expends financial resources, and impact is produced.3. to injecting inhibiter in oil well, solve CO
2corrosion is a kind of method of simple, convenience, less investment, instant effect.Nitrogen-containing organic compound, as imidazolines, organic amine, amides and their formed salt are widely used as inhibiter in the corrosion-resistant field of oil field.
Typical oilfield inhibiter is added in oil well between oil pipe and sleeve pipe by dropping mode, and the inhibiter adding relies on gravity and diffusion, enters into help and adopts solution.But add liquid inhibiter and have certain deficiency: 1) because oil well depth is larger, and inhibiter is diffused into liquid pumping hole place, is easily inhaled in oil pipe and returns to ground, cannot arrive shaft bottom, thereby cannot effectively protect carbon steel tube wall; 2) the corrosion inhibition timeliness of inhibiter is short; 3) liquid inhibiter consumption is large, causes financial loss.For above-mentioned deficiency, research and development solid corrosion inhibitor is necessary.
Sodium alginate (Sodium Alginate) is the natural polysaccharide being present in phaeophyta, is the linear chain anionic polymer of a class that beta-D-mannuronic acid (M) and α-L-guluronic acid (G) are connected to form by sugar former times key.Both the polymerization in homogeneous phase fragment (as MM, GG) that had existed each composition in its chain link, also exists heterogeneous polymerization fragment (as MG).When sodium alginate is met divalent cation, as Ca
2+, Co
2+, Ba
2+and Cu
2+deng, can there is ionotropy in it, change into not only there is strength property but also have elastic gel (a kind of between solid-state and liquid between state).Research shows: the most applicable formation gel of sodium alginate that guluronic acid (G) content is high.When the ratio of M and G reduces in sodium alginate chain link, be cross-linked to form the required Ca of gel
2+amount can corresponding increase.Based on sodium alginate nontoxicity and the characteristic that can generate gel, it is widely used as immobilization material and the pharmaceutical carrier of biologically active substance (as cell and enzyme) at present, and has huge actual application value just.Yet, have no and select alginate calcium as the report of the liquid inhibiter material of package curing.Based on the above fact, develop new inhibiter encapsulation technology, for solving the inhibiter that oil well occurs, cannot sedimentation to bottom facility, play the problem of effective provide protection, necessary.
Existing solid corrosion inhibitor, Chinese patent discloses CN1594659A raw material and mainly with high-carbon alkylamine surfactant, triethylene tetramine, trolamine, Sodium hexametaphosphate 99, the injection moulding of polyethylene synthetic intermediate, forms; Chinese patent mainly be take raw material diprotic acid, divinyl three ammoniums, Mono Chloro Acetic Acid and Sodium dodecylbenzene sulfonate, hexamethylenetetramine etc. for No. CN1912188A and is uniformly mixed the rear cooling mould molding of pouring into as heating raw materials; It is that Tianjin promise fourth, urotropine, thiocarbamide, benzotriazole and tensio-active agent crushing, stirring form that Chinese patent discloses CN101608313A main raw material; It is that stearic acid, calcium stearate, inhibiter, tensio-active agent and microorganism mix and be heated to 115 ℃ and become liquid state and then inject mold cools down moulding that Chinese patent discloses CN102337112A raw material; In CN103014718A, use the organic salt of oleic acid, tetraethylene pentamine, Bulbus Allii quintessence oil, the synthetic host of gum arabic high temperature and sodium-acetate or Tetrabutyl amonium bromide to mix the extrusion molding of injection mould.The organic raw material that above synthesis of solid inhibiter method adopts is many, and environment is had to certain pollution, and preparation technology needs the conditions such as high temperature, economical not.
summary of the invention:
The present invention aims to provide a kind of preparation method who solves oil well corrosion controllable release solid corrosion inhibitor, overcomes the deficiency of existing solid corrosion inhibitor described above.And then strengthened the protective effect of inhibiter to oil well portion facility.The desired raw material of solid corrosion inhibitor of the present invention is few, environmentally friendly, preparation method is simple, new technology, economical and practical, the alginate calcium solid corrosion inhibitor good mechanical property that contains weighting agent and inhibiter of preparation, sedimentation and release performance are good, can adapt to oil well and help the environment of adopting water high temperature, high pressure, high salinity.
The technical scheme that the present invention adopted is for achieving the above object: a kind of solution oil well corrosion controllable release solid corrosion inhibitor, it is microspheroidal or bar-shaped capsule, by the alginate calcium with flourishing duct as carrier, be present in the weighting agent that accounts for capsule total mass per-cent 10%～65% in carrier duct, with be present in the solid-state inhibiter that accounts for capsule total mass per-cent 20%～80% in carrier duct and form, wherein said weighting agent adopts BaSO
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder; Inhibiter is oil field conventional liq inhibiter, be prepared into capsule after liquid inhibiter be cured.
Described capsule shape is spherical or bar-shaped, circular capsule diameter 0.5 mm～30 mm.
A kind of preparation method who solves oil well corrosion controllable release solid corrosion inhibitor of the present invention, concrete technology comprises:
The first step, use liquid inhibiter dissolution with solvents sodium alginate:
In the time of 65～85 ℃, sodium alginate and liquid Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, according to mass ratio 1:20-30, are stirred to 30min～2h and mix, finally form uniform and stable viscous liquid; In this process, by container sealing, prevent inhibiter volatilization;
Second step, interpolation weighting agent
By the weighting agent BaSO of order number 100～500
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder, joins in above-mentioned viscous liquid according to the mass ratio of sodium alginate and weighting agent 1:1.5～10, stir 30 min～2 h, weighting agent is dispersed in liquid, forms new uniform liquid;
The 3rd step, use orifice device are prepared capsule
The uniform liquid making in second step is added drop-wise to the CaCl of mass concentration 2%～4% by orifice device
2precipitation bath in, after coagulation reaction 5～10 min, form wet microspheres capsule, after drying, can make dry capsule.
The described the first step, use liquid corrosion inhibitor solution to dissolve sodium alginate, its Raw sodium alginate adopts the currently available products of purchasing; Wherein inhibiter is liquid, in precipitation bath, has necessarily and retains, and adopts circulation packaged type to be used, and reduces the waste of inhibiter.
Described second step, use BaSO
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder, wherein BaSO
4the currently available products that employing is purchased, or adopt concentration lower than the BaCl of 0.5mol/L
2, Na
2sO
4replacement(metathesis)reaction occurs under solution stirring to be precipitated through 60 ℃ of dry 12 h and to make; CaCO wherein
3the currently available products that employing is purchased, or adopt concentration lower than the CaCl of 0.5mol/L
2, Na
2cO
3replacement(metathesis)reaction occurs under solution stirring to be precipitated through 60 ℃ of dry 12 h and to make.The addition of weighting agent directly has influence on the settling property of capsule microballoon.
Described the 3rd step, use orifice device are prepared capsule, wherein drip height distance precipitation bath liquid level 10～40 cm, prepare capsule of uniform size; The orifice device aperture of using has determined the particle diameter of capsule, can control capsule size, finally obtains the diameter of circular capsule at 0.5～30 mm.
Solid corrosion inhibitor using method of the present invention:
Solid corrosion agent capsules is directly added in the annular space between oil pipe and sleeve pipe.Solid corrosion agent capsules is immersed in to help and adopts in the aqueous solution, constantly sinks, and in settling process, discharges gradually inhibiter, arrives bottom and still can discharge, thereby effectively protect oil well equipment from top to bottom.
Unusual effect of the present invention is, compared with prior art, raw materials used few, environmentally friendly, preparation method is simple, reaction temperature and, comprehensive benefit is high.Can realize the encapsulation sedimentation of liquid inhibiter.Because sodium alginate is dissolved in corrosion inhibitor solution, be mixed to form uniform liquid with inhibiter, can improve encapsulation amount.In addition, the interpolation of weighting agent can improve the settling property of capsule greatly, for inhibiter is deposited to oil well bottom, provides important support.The present invention also can cannot sedimentation at other inhibiter field apply.Meanwhile, packed inhibiter volume after solidifying reduces, and adding of weighting agent is equal to the increase of inhibiter weight, is more conducive to sedimentation.The inhibiter of encapsulation is different with the diffusion of liquid inhibiter, can pass through alginate calcium duct, slowly discharges, thereby realizes controllable release.The micro encapsulation of inhibiter can also well solve the special corrosive environment in oil field may cause inhibiter spoilage problems, makes inhibiter keep corresponding stability, and corrosion inhibition is not fully exerted.
When preparing capsule, carrier adopts sodium alginate, and sodium alginate is a kind of marine algae that is extensively present in, especially the acidic anionic polysaccharide of the phaeophyta such as sea-tangle, sargassun plant, belong to natural macromolecular material, nontoxicity and can generate gel, precipitation bath reaction generates porous alginate calcium.
The present invention is in order to realize sedimentation and the release of inhibiter, and gordian technique one is adding of weighting agent, makes capsule have enough density, be conducive to microspheres capsule sedimentation, the 2nd, liquid inhibiter is encapsulated in capsule, along with capsule together sedimentation, and discharge inhibiter.Through test, capsule of the present invention, 70 ℃ are added to CO
2in saturated 3.5%NaCl solution, capsule, from swelling to fragmentation, discharges inhibiter gradually, and inhibiter works to oil field common oil sleeve pipe material P110, when the time of adding is 48 h, compares with blank sample, and corrosion electric current density is from 131 μ Acm
-2be reduced to 9.6 μ Acm
-2, slowly-releasing efficiency brings up to 92.7%, and corrosion mitigating effect is obvious.The present invention uses inhibiter encapsulation technology; for solving the inhibiter that oil well occurs, cannot sedimentation to bottom facility, play the problem of effective provide protection; method is novel; simple to operate; economical and practical, energy consumption is low, is applicable to amplify produce; the capsule good mechanical property of preparation, can adapt to oil field and help the environment of adopting water high temperature, high pressure, high salinity.
To sum up advantage of the present invention is:
1. capsule preparation method thereof is simple, and method is novel, and simple to operate, raw materials used few, environmentally friendly, economical and practical, energy consumption is low, is applicable to amplify produce.
2. capsule inhibiter encapsulation amount is large, can reach 20～80%.
3. the inhibiter release performance of capsule is good, can controllable release.
4. slowly-releasing efficiency is high, can reach more than 90%.
5. capsule settling velocity can regulate by the addition of weighting agent.
6. capsule good mechanical property, can adapt to oil field and help the environment of adopting water high temperature, high pressure, high salinity.
accompanying drawing explanation:
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the orifice device sketch that the present invention produces capsule microballoon, 1 orifice device in figure, 2 precipitation bath.
Fig. 2 is the dry wet capsule finished product making.
Fig. 3 is the settling velocity of dry wet capsule.
Fig. 4 is that capsule discharges inhibiter graphic representation.
Fig. 5 is metamorphosis figure in microspheres capsule settling process.
Fig. 6 is the conventional material P110 test piece polarization curve of oil well casing.
Fig. 7 is P110 test piece surface picture: when in figure, 70 ℃ of (a) P110 test pieces (b) add inhibiter and soak 70 ℃ of 1 h (c), inhibiter does not exist and soaks 48 h.
embodiment:
Below for specific embodiment, introduce in detail content of the present invention, it is for the ease of understanding the present invention that embodiment is provided, and is never the invention of restriction this patent.
Embodiment 1
A kind of solution oil well corrosion controllable release solid corrosion inhibitor, the circular capsule of diameter 1.5 mm, as carrier, is present in carrier duct 20% weighting agent by the alginate calcium with flourishing duct, form with the inhibiter that is present in carrier duct 70%, wherein said weighting agent adopts BaSO
4; Inhibiter is the conventional liq inhibiter tetrahydroglyoxaline quaternary amine that existing oil field is used.
Concrete technology preparation process comprises:
The first step, use liquid inhibiter to dissolve sodium alginate
In the time of 70 ℃, sodium alginate is mixed according to mass ratio 1:30 with liquid Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, stir 30 min, finally form uniform and stable viscous liquid; In this process, by container sealing, prevent inhibiter volatilization.Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor used is the conventional inhibiter in oil field.
Second step, interpolation weighting agent
By the Powdered BaSO of order number 300
4, according to the amount calculating, joining in thick liquid and stir 1 h, weighting agent is dispersed in liquid, forms new uniform liquid.
The 3rd step, use orifice device are prepared capsule
Adopt orifice precipitation bath legal system for capsule, Fig. 1 is shown in by experimental installation.Concrete operations are that the liquid making in second step is added drop-wise to 4% CaCl with orifice device 1
2precipitation bath 2 in, drip height distance precipitation bath liquid level approximately 10 cm, reaction is solidified after 5 min, uses filter screen to take out wet microspheres capsule, the 60 ℃ of ventilations on gauze that minute intersperse among are dried.Fig. 2 is shown in by the wet and dry bulb making, wet bulb diameter 4 mm, dry bulb diameter 1.5 mm.
Embodiment 2
A kind of solution oil well corrosion controllable release solid corrosion inhibitor, the circular capsule of diameter 4 mm, as carrier, is present in carrier duct 45% weighting agent by the alginate calcium with flourishing duct, form with the inhibiter that is present in carrier duct 30%, wherein said weighting agent adopts CaCO
3; Inhibiter is the conventional liq inhibiter that existing oil field is used.
Concrete technology preparation process comprises:
The first step, use liquid inhibiter to dissolve sodium alginate
In the time of 80 ℃, sodium alginate is mixed according to mass ratio 1:20 with liquid Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, stir 2 h, finally form uniform and stable viscous liquid; In this process, by container sealing, prevent inhibiter volatilization.Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor used is the conventional inhibiter in oil field.
Second step, interpolation weighting agent
By the Powdered CaCO of order number 200
3, according to joining in thick liquid, stirring 2 h, weighting agent is dispersed in liquid, forms new uniform liquid.
The 3rd step, use orifice device are prepared capsule
Adopt orifice precipitation bath legal system for capsule, Fig. 1 is shown in by experimental installation.Concrete operations are that aperture is 5 mm by the liquid making in second step orifice device, are added drop-wise to 2% CaCl
2precipitation bath in, drip height distance precipitation bath liquid level approximately 20 cm, reaction is solidified after 10 min, uses filter screen to take out wet capsule, 60 ℃ of ventilations are dried, and obtain the dry bulb of diameter 4 mm.
Embodiment 3
A kind of solution oil well corrosion controllable release solid corrosion inhibitor, the circular capsule of diameter 25 mm, as carrier, is present in carrier duct 30% weighting agent by the alginate calcium with flourishing duct, form with the inhibiter that is present in carrier duct 60%, wherein said weighting agent adopts zinc powder; Inhibiter is the conventional liq inhibiter that existing oil field is used.
Concrete technology preparation process comprises:
The first step, use liquid inhibiter to dissolve sodium alginate
In the time of 70 ℃, sodium alginate is mixed according to mass ratio 1:26 with liquid Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, stir 1 h, finally form uniform and stable viscous liquid; In this process, by container sealing, prevent inhibiter volatilization.Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor used is the conventional inhibiter in oil field.
Second step, interpolation weighting agent
By the Powdered zinc powder of order number 300, according to the amount calculating, join in thick liquid and stir 1 h, weighting agent is dispersed in liquid, forms new uniform liquid.
The 3rd step, use orifice device are prepared capsule
Adopt orifice precipitation bath legal system for capsule, Fig. 1 is shown in by experimental installation.Concrete operations are by the liquid making in second step orifice device, and aperture 30 mm are added drop-wise to 2% CaCl
2precipitation bath in, drip height distance precipitation bath liquid level approximately 35 cm, reaction is solidified after 10 min, uses filter screen to take out wet capsule, 60 ℃ of ventilations are dried, and obtain the dry bulb of diameter 25 mm.
For product of the present invention is carried out to performance verification, carried out following test:
Test 1
In order to test circular capsule settling property, record the impact of different weighting agent additions on the settling velocity of dry, wet capsule, dry, wet capsule settling velocity is shown in Fig. 3 with weighting agent encapsulation amount changing conditions.For the sample of identical weighting agent encapsulation amount, the settling velocity of dry bulb is obviously greater than wet bulb, therefore, adopts dry bulb to carry the sedimentation that inhibiter is conducive to inhibiter, and actual adding considers to use dry bulb.The settling velocity of dry bulb and wet bulb is consistent with the trend of weighting agent encapsulation quantitative change in addition, and capsule settling velocity all increases and increases gradually with encapsulation amount.
Test 2
For the release performance of test capsule, utilize ultraviolet-visible pectrophotometer to detect the burst size of inhibiter over time, result as shown in Figure 4, is as can be seen from the figure tested starting stage inhibiter and is discharged rapidly.In the time of 70 ℃, after standing 4 h, it is maximum that capsule degree of swelling reaches, and after swelling 12 h, capsule starts to occur fragmentation, and final complete fragmentation causes inhibiter to discharge completely, but because inhibiter has volatility, so the complete broken rear burst size of capsule is lower than 100%.In addition, the burst size of 15 ℃ of inhibiter obviously reduces by 70 ℃, and when temperature is lower, capsule is being difficult to fragmentation after 12 h swellings.In conjunction with capsule settling property, provide the changing conditions in oil well in capsule settling process and see Fig. 5.While starting to throw in, microspheres capsule is shrivelled roundlet capsule, and the liquid level that enters oil well solution is dark apart from the about 700m in ground, as Fig. 5 (a).Along with immersing in solution, absorbent solution, capsule starts swelling and discharges inhibiter, and 4 h degree of swelling are maximum, and as Fig. 5 (b), now capsule is deposited to apart from ground 1200～1500m degree of depth, and capsule continues sedimentation.Due to acidity and temperatures involved, capsule starts fragmentation, as Fig. 5 (c) has incomplete broken capsule at well depth 1700～2000 places, exists, and while arriving shaft bottom, will have many broken capsules.Capsule constantly discharges inhibiter in shattering process.Broken capsule is (approximately 2500～3000m) for some time in shaft bottom, completely broken, as Fig. 5 (d) inhibiter also discharges completely.
Test 3
CO is put in 70 ℃ of oil field common oil sleeve pipe material P110 carbon steel test pieces
2in saturated 3.5%NaCl solution, capsule microballoon is added in this solution.Capsule sinks under solution, from swelling to fragmentation, discharges gradually inhibiter, inhibiter is the conventional imidazoline-ammonium-salt in oil field, and along with inhibiter discharges, the corrosion electric current density of test piece reduces gradually, when the time of adding is 48 h, to compare with blank sample, corrosion electric current density is from 131 μ Acm
-2be reduced to 9.6 μ Acm
-2, slowly-releasing efficiency brings up to 92.7%, the obvious (see figure 6) of corrosion mitigating effect.Corrosion potential E shuffles and illustrates that Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor is anodic corrosion inhibitor, and the increase of density of corrosion inhibitor, and the solidity to corrosion tendency of test piece is increased.There is lone-pair electron absorption test piece surface on nitrogen-atoms in inhibiter, forms layer protecting film, and test piece is had to good barrier propterty.
Fig. 7 is the photo on P110 carbon steel test piece surface.Test piece after pre-treatment, surface-brightening, has metalluster, and test piece is not soaked 1 h in 70 ℃ add corrosion inhibitor solution, and test piece surface just generates one deck black corrosion product, and product quality is more loose, with FeCO
3for main component; And test piece is soaked after 48 h in 70 ℃ of inhibiter exist solution, surface changes not obvious, shows that inhibiter is obvious to P110 carbon steel test piece protection effect.The result that this and Fig. 6 polarization curve are tested matches.
The performance test of test 1-3 is all at CO
2in saturated 3.5%NaCl solution, carry out.
Above-mentioned concrete embodiment is for feature of the present invention is described; case study on implementation has been introduced the design of invention; experimental technique, performance test methods; but can not limit claim of the present invention, other is any does not deviate within technical scheme of the present invention is included in protection scope of the present invention.
Claims (6)
1. one kind solves oil well corrosion controllable release solid corrosion inhibitor, it is characterized in that: by the alginate calcium with flourishing duct as carrier, be present in the weighting agent that accounts for capsule total mass per-cent 10%～65% in carrier duct, with be present in the solid-state inhibiter that accounts for capsule total mass per-cent 20%～80% in carrier duct and form, wherein said weighting agent adopts BaSO
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder; Raw material inhibiter is the conventional liq inhibiter that oil field is used, be prepared into capsule after liquid inhibiter be cured.
2. a preparation method who solves oil well corrosion controllable release solid corrosion inhibitor, is characterized in that: concrete technology comprises:
The first step, use liquid corrosion inhibitor solution to dissolve sodium alginate:
In the time of 65～85 ℃, sodium alginate and liquid Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, according to mass ratio 1:20-30, are stirred to 30min～2h and mix, finally form uniform and stable viscous liquid; In this process, by container sealing, prevent inhibiter volatilization;
Second step, interpolation weighting agent
By the weighting agent BaSO of order number 100～500
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder, joins in above-mentioned viscous liquid according to the mass ratio of sodium alginate and weighting agent 1:1.5～10, stir 30 min～2 h, weighting agent is dispersed in liquid, forms new uniform liquid;
The 3rd step, use orifice device are prepared capsule
The uniform liquid making in second step is added drop-wise to the CaCl of mass concentration 2%～4% by orifice device
2precipitation bath in, after coagulation reaction 5～10 min, form wet microspheres capsule, after drying, can make dry microspheres capsule.
3. a kind of solution oil well corrosion controllable release solid corrosion inhibitor according to claim 1, is characterized in that: described capsule shape is spherical or bar-shaped ball-type capsule diameter 0.5 mm～30 mm.
4. a kind of preparation method who solves oil well corrosion controllable release solid corrosion inhibitor according to claim 2, is characterized in that: the described the first step, use liquid corrosion inhibitor solution to dissolve sodium alginate, its Raw sodium alginate adopts the currently available products of purchasing; Wherein inhibiter is liquid, in precipitation bath, has necessarily and retains, and adopts circulation packaged type to be used, and reduces the waste of inhibiter.
5. a kind of preparation method who solves oil well corrosion controllable release solid corrosion inhibitor according to claim 2, is characterized in that: described second step, use BaSO
4, titanium-iron powder, sparring powder, CaCO
3or the metal powder such as zinc powder, iron powder is as weighting agent, BaSO wherein
4the currently available products that employing is purchased, or adopt concentration lower than the BaCl of 0.5mol/L
2, Na
2sO
4replacement(metathesis)reaction occurs under solution stirring to be precipitated through 60 ℃ of dry 12 h and to make; CaCO wherein
3the currently available products that employing is purchased, or adopt concentration lower than the CaCl of 0.5mol/L
2, Na
2cO
3replacement(metathesis)reaction occurs under solution stirring to be precipitated through 60 ℃ of dry 12 h and to make.
6. a kind of preparation method who solves oil well corrosion controllable release solid corrosion inhibitor according to claim 2, it is characterized in that: described the 3rd step, use orifice device are prepared capsule, wherein drip height distance precipitation bath liquid level 10～40 cm, prepare capsule of uniform size; The orifice device aperture of using has determined the particle diameter of capsule, can control capsule size.
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| CN105199697A (en) * | 2015-10-22 | 2015-12-30 | 中国海洋石油总公司 | Oil well solid anti-scaling corrosion inhibitor and preparation method thereof |
| CN105441043A (en) * | 2014-08-11 | 2016-03-30 | 中国石油天然气股份有限公司 | Temporary plugging microsphere and preparation method thereof |
| CN106904603A (en) * | 2017-03-03 | 2017-06-30 | 青岛农业大学 | A kind of corrosion inhibiter microcapsules based on graphene roll and preparation method thereof |
| CN107304078A (en) * | 2016-04-20 | 2017-10-31 | 武汉理工大学 | A kind of environmentally friendly delayed release polymeric thing antisludging agent and preparation method thereof |
| CN109266316A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of drilling fluid thickening extracting and cutting agent resistant to high temperatures and preparation method thereof and drilling fluid |
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| CN109762546A (en) * | 2019-01-28 | 2019-05-17 | 西南科技大学 | A kind of preparation method of the acrylamide being loaded with corrosion inhibiter-bentonite capsule |
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| CN110863208A (en) * | 2019-12-04 | 2020-03-06 | 哈尔滨工业大学（威海） | Carbon steel pickling corrosion inhibitor based on polygonatum polysaccharide |
| CN111236889A (en) * | 2020-03-30 | 2020-06-05 | 中国石油天然气集团有限公司 | Oil well underground delayed dosing device and using method thereof |
| CN112063376A (en) * | 2020-08-20 | 2020-12-11 | 汉中聚智达远环能科技有限公司 | Solid corrosion inhibition capsule for oil extraction and preparation method and application method thereof |
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| CN110863208B (en) * | 2019-12-04 | 2022-08-09 | 威海创惠环保科技有限公司 | Carbon steel pickling corrosion inhibitor based on polygonatum polysaccharide |
| CN111236889A (en) * | 2020-03-30 | 2020-06-05 | 中国石油天然气集团有限公司 | Oil well underground delayed dosing device and using method thereof |
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| CN113717706A (en) * | 2021-08-05 | 2021-11-30 | 西安交通大学 | Preparation method of completely degradable solid corrosion inhibitor |
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