CN1234821A - Corrosion inhibitor for wellbore application - Google Patents
Corrosion inhibitor for wellbore application Download PDFInfo
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- CN1234821A CN1234821A CN 96180471 CN96180471A CN1234821A CN 1234821 A CN1234821 A CN 1234821A CN 96180471 CN96180471 CN 96180471 CN 96180471 A CN96180471 A CN 96180471A CN 1234821 A CN1234821 A CN 1234821A
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Abstract
This invention concerns a corrosion-inhibitor nominally comprised of a phenolic compound and a hydroxide-bearing compound capable of imparting a pH of 9 to water, the inclusion thereof in aerated water-based fluids and foams, and the use of these fluids in wellbore applications; particularly applications conducted at elevated temperature.
Description
Background of invention
The present invention relates to a kind of corrosion inhibitor and the purposes in the application in well.
The liquid of inflation and foam are used as in-hole fluid usually during drilling well, completion, arrangement and extraction operation.Inflation used herein means and has gas phase and liquid phase separately.Aerated liquid can be different from foam because of the tensio-active agent that does not have or exist the alternate dispersibility of very a spot of promotion solution-air.
Liquid and the foam particularly suitable inflated when need reducing static pressure in the well.Because aerated liquid and foamy tap density are lower than their liquid counterpart, so can reduce static pressure or statical head.Wish that the example that reduces statical head comprises: (1) in-hole fluid is exposed to the geological stratification of negative pressure and requires the occupy minimum situation of in-hole fluid to the stratum, (2) in uneven condition (being that borehole pressure is lower than hydrodynamicpressure in the geological stratification of exposure) down during the boring of geological stratification, wherein reduce pressure head help to reduce to greatest extent because of fines move in the hole in the well due to stopple stifled.
Aerated liquid is made up of gas and liquid usually, also can contain solid such as the mud and the sand of additive such as corrosion inhibitor and suspension.Be applicable to that the aerated fluid in drilling well, completion, arrangement and the extraction operation typically is mixed with by the down-hole of gas and liquid.In drilling well, a kind of mode that these components are mixed in the down-hole is to utilize two drill set and dual rotary joint.The another kind of mode that is usually used in borehole operation is to use sends gas into the attached pipe that injection down-hole point and liquid mixing are returned the surface again.Any position injected gas is used to reduce the statical head in shaft bottom in the down-hole, descends from 100% liquid head.Also carry out the mine gas injection when exploiting with gas lift slab hole inner fluid.Foam is the solution-air two-phase system of gas high dispersing in liquid.Physically foam is made up of the bubble that the moisture film that is contained tensio-active agent surrounds, nominally be made up of gas, at least a tensio-active agent (as whipping agent) and water.The foamy quality definition is the percentage by volume of gas in the two-phase mixture.Used water can be chemical pure, fresh in the foam, or contains in various degree salinity and/or hardness.Foam also can contain other additive of the foaming properties that changes.These additives comprise the polymkeric substance and/or the wilkinite of selection, thereby it increases film toughness formation thickness or agglomerative foam; Be used for reducing the corrosive corrosion inhibitor of foam in metallic system.
The foamy rheological is very complicated, provides unique basis for distinguishing foam and inflation and unaerated liquid.Rheological and many parameter correlations are as the concentration and the type of foam size and distribution, fluid viscosity, froth quality and used whipping agent.Replace conventional fluid generally to reduce fluid with foam and in well, invade the degree on stratum on every side.In addition, the foam of invading the stratum generally contains the gas of high percentage by volume, and very big energy is arranged during pressurization.During decompression, discharge energy stored and cause most of fluid to return in the well.Compare with conventional fluid, foam still has fabulous carrying capacity under low linear rate of flow, particularly for water and solid.These performance particularly suitables when carrying out drilling well, completion and housekeeping operation on vertical and horizontal well run into these performances even more suitable when forming low pressure, half depletion or water-sensitive strata.The foamy special performance also can use the coiled tubing device during housekeeping operation.Use this device can under the situation of not removing pipe in the well, carry out obviously saving time and saving money because of downhole operations.
In the past, using aerated liquid and foamy subject matter is metallic corrosion, owing to having oxygenant such as oxygen, hydrogen sulfide and carbonic acid gas in the gas phase.Oxygen is generally from air.Carbonic acid gas and hydrogen sulfide are generally produced by the geological stratification of being concerned about.It is more serious that etching problem generally becomes along with the increase of well temperature.Because cost and availability, air is preferred gaseous matter when downhole corrosion is out of question.Yet, lack suitable corrosion inhibitor when (be high temperature and have a large amount of oxygenants) because that conditions down-hole becomes is harsh, so often use expensive rare gas element, the most frequently used is nitrogen.
Summary of the invention
One of purpose of the present invention is a kind of corrosion inhibitor that is applicable to gas-liquid system under oxidizing condition of exploitation.
Another object of the present invention is a kind of inhibition corrosive solution-airmixture that is adapted at use under the oxidizing condition of exploitation.
A further object of the present invention is a kind of inhibition corrosive foam that is adapted at use under the oxidizing condition of exploitation.
Another purpose more of the present invention is that a kind of being applicable to of exploitation used the inhibition corrosive oxygen-containing gas/liquid mixture that comprises in drilling well, arrangement, completion and the exploitation in the well.
Another purpose more of the present invention is a kind of being adapted at least about the inhibition corrosive air/liquid mixture that uses under 200 the temperature of exploitation.
Another purpose more of the present invention is a kind of inhibition corrosive oxygen-containing gas/liquid mixture of exploitation, and the chemical substance of wherein giving corrosion-inhibiting is inexpensive relatively commercial chemistry material.
Another purpose more of the present invention is a kind of using method of foam in drilling well, completion, arrangement and exploitation of using under the high oxidation condition of being adapted at of exploitation.
According to the present invention, find a kind of prescription of corrosion inhibitor, form by phenolic compound and the compound hydroxy that contains that can make water give alkalescence.
In second embodiment, find a kind of inhibition corrosive gas-liquid mixture, nominally by gas, water, phenolic compound and can make water give alkalescence the compound hydroxy that contains form.
In the 3rd embodiment, find a kind of new inhibition corrosive gas foam, nominally be made up of gas, water, whipping agent and corrosion inhibitor, described corrosion inhibitor is made up of phenolic compound and the compound hydroxy that contains that can make water give alkalescence.
In the 4th embodiment, find to use under a kind of oxidizing condition that exists under oxidizing condition, using in as well the method for solution-airmixture of the present invention.
In the 5th embodiment, find to use foamy method of the present invention under a kind of oxidizing condition that exists under oxidizing condition, using in as well.
Detailed Description Of The Invention
In multiple embodiments, the present invention relates to a kind of unique formula of corrosion inhibitor, a kind of prescription that suppresses the corrosive aerated liquid, a kind of suppress corrosive foamy prescription, and the liquid or the foam of inflation in well, use the purposes that comprises in drilling well, arrangement, completion and the extraction operation.
Corrosion inhibitor
Nominally corrosion inhibitor of the present invention comprises that by at least a phenolic compound its salt and at least a pH of water that can make form at least 9 the compound hydroxy that contains.The hydrocarbon compound of hydroxyl is preferably the phenolic compound of following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
Another group compound that is included in the term phenolic compound is yellow tannins (flavotannins).Yellow tannins is the polyphenols that is extracted by bark and trees.Quebracho is an example of the yellow tannin that is suitable for.
The representative example of the phenolic compound that is suitable for is to be selected from monohydroxy phenol, polyhydroxy phenol, the monohydroxy naphthols, the poly-hydroxy naphthols, Ortho Cresol, m-cresol, p-cresol, adjacent fluorophenol, m fluorophenol, p-fluorophenol, ortho chloro phenol, m-Chlorophenol, para-chlorophenol, adjacent bromophenol, between bromophenol, p bromophenol, phenol o-iodine, between iodophenol, to iodophenol, o-NP, m-nitrophenol, p-NP, yellow tannin, phenol, Resorcinol, pyrocatechol, quinhydrones, Phloroglucinol, 1,2, the 3-benzenetriol, 1, the 3-dihydroxy naphthlene, hydroxyanisole, p methoxy phenol, meta-methoxy phenol, salicylic acid, P-hydroxybenzoic acid, m-Salicylic acid, o-phenyl phenol sulfonic acid, the p-phenolsulfonic acid, between sulfocarbolic acid, chlorophenesic acid, 4, the 4-biphenol, salicylic aldehyde, methyl catechol, with those phenolic compounds or its mixture of above-mentioned acid with the salt of alcohol.
Phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde, Phloroglucinol, 1 more preferably, 2,3-benzenetriol, 4,4-biphenol, 1,3-dihydroxy naphthlene or o-allyl phenol, or the mixture of the salt of above-claimed cpd or above-claimed cpd.Also more preferably be selected from the mixture of phenol, Ortho Cresol, salicylic aldehyde, o-NP and ammonium thereof, sodium and sylvite or above-claimed cpd.Most preferred phenates is sodium and sylvite.Based on performance, cost and commercially available property, most preferred phenolic compound is phenol and sodium and sylvite, i.e. sodium phenylate and potassium phenylate.
It is described that to contain compound hydroxy must be that to make the pH of water be 9 compound.Preferably containing compound hydroxy is alkali metal hydroxide, ammonium hydroxide and composition thereof.More preferably be selected from those compounds of ammonium hydroxide, sodium hydroxide and potassium hydroxide.Certainly, sodium hydroxide and potassium hydroxide are more preferably.Potassium hydroxide most preferably.
Contain compound hydroxy must with guarantee with phenolic compound on the obvious dissociative significant quantity of hydrogen atom that links of hydroxyl exist.By mole, the mol ratio that contains compound hydroxy and phenolic compound is preferably 5 to 1000, and more preferably from about 10 to about 500, and most preferably from about 20 to about 350.Use by ammonium hydroxide, potassium hydroxide or sodium hydroxide or its mixture form preferably contain compound hydroxy and most preferred phenolic compound-phenol the time, the weight ratio of oxyhydroxide and phenol is preferably about 10 to about 70.When using preferred sodium hydroxide and potassium hydroxide, preferred weight ratio is about 10 to about 40.
Corrosion inhibitor also can contain the water of significant quantity, thereby as phenolic compound with contain the dispersion agent of compound hydroxy or carrier the mixing of these compounds and other component when simplifying preparation aerated liquid or foam.This water can be chemical pure, fresh or contain tangible salt concn and/or hardness, can contain the solution gas of easy generation oxygenizement.
Corrosion inhibitor of the present invention and many other inhibitor particularly difference of scavenging agent are still can play a role effectively when the mol ratio of crucial active ingredient-phenolic compound and oxygenant in the system is starkly lower than 1.This corrosion inhibitor is all effective under environment and intensification.Inhibitor of the present invention and many differences that is purchased inhibitor also are it at least about the validity under 200 the temperature, and further difference is that it still has superior corrosion-inhibiting under at least about 350 temperature.When oxygenant was oxygen or its compound relevant with oxidation, this corrosion inhibitor was effective especially.
Suppress the corrosive aerated liquid
Found to suppress the corrosive aerated liquid and various application have been arranged as in-hole fluid.Nominally aerated liquid is made up of the gas that contains oxygenant, water and foregoing corrosion inhibitor of the present invention.As previously described, when oxygenant was hydrogen sulfide, carbonic acid gas and oxygen or these reagent compound relevant with oxidation, this corrosion inhibitor was effective especially.Preferably treatment contains the aerated liquid of oxygen as oxygenant.Described water can be chemical pure, fresh or contain tangible salt concn and/or hardness that can contain dissolved gases, oxygenizement may easily take place some of them.Aerated liquid also can contain solid as husky and mud or independent organic phase.
When needing to reduce the tap density of stoste, the liquid particularly suitable of inflation.Need to reduce statical head in well, using these needs are arranged often.
Aerated liquid is mixed gas, water fluid and the corrosion inhibitor preparation that contains at least a oxygenant with techniques well known.Preferably, mix water fluid and corrosion inhibitor earlier and form inhibition corrosive liquid.Liquid is contacted with gas phase add gas.In the exploitation of drilling well, completion, arrangement or well, back one contact procedure is carried out in the down-hole with techniques well known usually.
Corrosion inhibitor also can be used for using the exploitation of the well of gas lift technology.In this used, corrosion inhibitor can mix in the down-hole with the aqueous fluid of gas that is used for gas lift and production.In this uses, reduce statical head can with existing pressure accumulation make the fluid (also may comprise independent gas phase) of savings as motivating force thus flowing to the surface avoids using more complicated and expensive quarrying apparatus such as pump screw block (pumpjacks), submersible pump etc.In this operation, the compound that gaseous oxidizer such as hydrogen sulfide, carbonic acid gas or oxygen and these reagent are relevant with oxidation can be present in the gas that is used for gas lift or be present in the savings fluid that is produced.
Required corrosion inhibition agent concentration is to guarantee to suppress the corrosive significant quantity in the time range of being concerned about under the condition of being concerned about in the aerated fluid.Those skilled in the art can easily determine these concentration with conventional test method.Usually, by the preferred weight percentage of the compound of the hydrogeneous oxygen root of total restatement of water and corrosion inhibitor and phenolic compound be respectively about 0.1 to about 40% (weight) and about 0.005 to about 4.0% (weight).Preferred weight percent scope be respectively about 1 to about 20% (weight) and about 0.01 to about 0.50% (weight).Also preferred weight percent scope is respectively about 1 to about 10 and about 0.05 to about 0.30.Most preferred weight percent scope is respectively about 5 to about 10 and about 0.10 to about 0.30.
Corrosion inhibitor of the present invention and other inhibitor particularly a distinguishing characteristics of sanitising agent are: in the time of in mixing aerated liquid, inhibitor of the present invention can play a role effectively when the mol ratio of the oxygenant in crucial active ingredient-phenolic compound and the system is starkly lower than 1.Suppress the corrosive aerated liquid and can under environment and intensification, be used for metallic system.Inhibitor of the present invention and many another distinguishing characteristicss that is purchased inhibitor are its validity under about 200 or higher temperature, even still effective under about 350 or higher temperature.When oxygenant was oxygen or its compound relevant with oxidation, this corrosion inhibitor mixed in the aerated liquid effective especially.
Suppress the corrosive foam
Nominally the present invention suppress the corrosive foam by gas wherein contain the dispersion gas phase of oxygenant and continuously liquid phase form, nominally liquid phase is by whipping agent, form as the water and the corrosion inhibitor of the present invention of major portion.Described water can be chemical pure, fresh or contain tangible salt concn and/or hardness that can contain dissolved gases, oxygenizement may easily take place some of them gas.With those skilled in the art's wish, liquid phase can contain other additive and be used for producing the better foam of performance under working conditions.Suds-stabilizing agent is the one example.Foam also can contain solid as husky and mud and/or independent organic phase.
For the cumulative volume percentage of the gas-liquid phase of gas is defined as froth quality.Froth quality is preferably about 60 to about 99.75% under the condition in well, and more preferably from about 75 to about 99.5% (volume).Utilize various additive well known in the art can change the foamy performance.For example, adding guar gum or other organic polymer and solid such as wilkinite in basal component can prepare than the heavy-gravity foam.
The beginning gas phase can contain oxygenant or gas phase can be inert and absorb oxygenant such as oxygen, hydrogen sulfide or carbonic acid gas or the compound relevant with oxidation in operational process of craft.Since the validity of corrosion inhibitor of the present invention, when oxygen is oxidizing substance, oxygenous inhibition foam particularly advantageous.Because cost and availability, preferred gas phase mainly is made up of air.
To as described in the aerated liquid, need in the time range of being concerned about under the condition of being concerned about, guarantee to suppress the corrosion inhibitor of corrosive significant quantity as the front.Those skilled in the art can easily determine these concentration by the routine test method.Identical with those preferable range of reporting at aerated liquid based on the percentile preferable range of the gross weight of water, corrosion inhibitor and whipping agent, wherein said weight percent is by water and corrosion inhibitor.
Corrosion inhibitor of the present invention and other inhibitor particularly a distinguishing characteristics of scavenging agent are: when mixing in the foam, inhibitor of the present invention can play a role effectively when the mol ratio of the oxygenant in crucial active ingredient-phenolic compound and the system is starkly lower than 1.Suppress the corrosive foam and can under environment and intensification, be used for metallic system.The present invention suppresses another distinguishing characteristics of foamy that corrosive foam and many uses be purchased inhibitor and is to show under about 200 or higher temperature and suppresses the corrosive performance, even still shows predominant suppressing corrosive performance under about 350 or higher temperature.When oxygenant was oxygen or its compound relevant with oxidation, this corrosion inhibitor was effective especially.
Need acquisition to require the whipping agent of the significant quantity of froth quality.Concentration depends on the salt concn of water and the interior exposure condition of well of hardness, whipping agent and expectation.Those of ordinary skills are easy to select the reagent that is fit to and the concentration of described reagent.The test method that those skilled in the art use always comprises " oil and soap ", Vol.18,1941, p99-102 and " synthetic detergent ", author J.W.McCutcheon, McNair-Dorland Co., New York, NY, 1950, the Ross-Miles foam analysis method of being discussed among the p435; These two pieces of documents all are incorporated herein for reference.One class preferred blowing agent is Ross-Miles initial foam height 10cm and accumulation foam height those whipping agents of 30cm at least at least under test conditions, wherein accumulates the foam height sum of foam height for obtaining at 0,1,2,5 and 10 minute with the Ross-Miles method.Typical density of foaming agent is pressed the active foaming agent densitometer, for about 0.005 to about 4.0% (weight), based on the weight of water, corrosion inhibitor and whipping agent in the liquid phase.More preferably density of foaming agent is about 0.01 to about 1.0% (weight), based on liquid phase.Also preferred density of foaming agent is about 0.1 to about 0.3% (weight), based on liquid phase.
The multiple compound that is called tensio-active agent has the foamy of formation performance.These compounds are discussed at " Surfactants and Distersive Systems " as the habit of whipping agent, Kirk-Othmer Encyclopedia of Chemical Technology, the 3rd edition, volume 22, among the p332-387, the document is incorporated herein for reference.
Preferred blowing agent comprises following one or more:
(a) one or more N-acylsarcosine salt, more preferably one or more of following formula:
Wherein R is that cocoyl, lauryl or oleoyl and M are H or Na;
(b) one or more N-acyl group-N-alkyl taurine sodium, more preferably one or more of following formula:
Wherein R is cocoyl, palmitoyl or Yatall MA base;
(c) one or more alkyl sodium sulfate ester salt, more preferably one or more of following formula:
R-O-SO
3M
Wherein R is a lauryl, and M is positively charged ion or the alkali metal cation that contains ammonium, more preferably Na, Mg, K, NH
4, MEA (an ethanol ammonium), DEA (di-alcohol ammonium) or TEA (triethanol ammonium);
(d) one or more ethoxylation and sulfated alcohols, more preferably one or more of following formula:
Wherein n is 1-5, and M is positively charged ion or the alkali metal cation that contains ammonium, more preferably NH
4Or Na and R are linear C
12-14, linear C
12-15, lauryl, tridecyl, myristyl or octyl group-octyl group;
(e) one or more ethoxylation and sulfation phenol, more preferably one or more of following formula:
Wherein n is 1-5, and M is positively charged ion or the alkali metal cation that contains ammonium, more preferably NH
4Or Na and R are nonyl, octyl group or decyl;
(f) one or more fatty alcohol ethoxylate, more preferably one or more of following formula:
Wherein R is selected from C
6, C
8, C
9-11, C
10, C
10-12, C
12, C
12-14, C
14, C
12-15, C
16, and C
18Straight chain and branched-chain alkyl, isosteryl, lauryl, hexadecyl, stearyl, oil base, tridecyl, tallow base, trimethylammonium nonyl or isodecyl and n be 2 to 100;
(g) one or more amine oxide, the more preferably amine oxide of following formula:
Wherein R is hexadecyl, lauryl, myristyl, stearyl, cocoa base, hydrogenated-tallow group, hexadecyl, tallow base, octadecyl, decyl, C
8-10Oxygen propyl group (oxypropyl), C
9-11Oxygen propyl group or C
12-15The oxygen propyl group, and R ' is CH
3Or CH
2CH
2OH can be identical or different;
(h) one or more alkyl betaine more preferably has following formula:
Wherein R is cocoa base, decyl, hexadecyl, lauryl or oil base;
(i) one or more amido propyl betaine more preferably has the amido propyl betaine of following formula:
Wherein R is cocoa acyl (cocyl), lauroyl, isostearoyl, mnyristoyl, palmityl, and most preferably R is the cocoa acyl; Or
(j) one or more fluorine-containing tensio-active agent, more preferably fluorine albumen or fluoro aliphatics tensio-active agent.
Foam be exposed to be higher than 200 °F, when particularly being higher than 300 temperature, preferred blowing agent more preferably is made up of the aliphatic series or the alkaryl sulfonated hydrocarbon of one or more acyl aminopropyl trimethyl-glycine and one or more ethoxylation, sulfated alcohols or one or more following formula one or more acyl aminopropyl trimethyl-glycine:
R-SO
3M
Wherein R is that the oleophilic group of 10 to 18 carbon atoms and M are arranged is basic metal or ammonium cation.Most preferred whipping agent is made up of cocounut oil acyl aminopropyl trimethyl-glycine and sulfation glycol ether (activeconstituents among the Homco SF-1009).The preferred concentration of each component counts about 0.0025 to about 2.0% (weight) by the weight of water, corrosion inhibitor and whipping agent in the liquid phase in the above-mentioned two component whipping agent systems.More preferably each component concentrations is about 0.01 to about 2.0% (weight).Also more preferably each component concentrations is about 0.05 to about 0.15% (weight).Most preferably each component concentrations is about 0.08% (weight).
General with surface apparatus (facilities) preparation foam, the liquid that wherein will become the gas of disperse phase and will become external phase mixes in the turbulent flow mode.Usually, under " mix T " under turbulent-flow conditions mixed gas and liquid ingredient carry out this step.Second kind produces the foamy method is with enclosed appts separately liquids and gases to be flowed in the well respectively, makes gas and liquid mixing then in the down-hole, thereby produce foam in well.Described enclosed appts is that those skilled in the art are facile, comprises annular space and attached pipe between pipe, drillsteam, pipe or drillstream and wall or the casing in the well.In the third method, by gas and liquid in well up and down and stream and in well, produce foam.Good foam generally has the denseness of shaving cream.
In a preferred method, produce foam on the surface, thereby form in foam and pipe that injects into well or the annular space by close mixed gas and liquid.Pipe or annular space recovery well inner fluid by non-injection.Foamy speed depends on operation types in the well, and designing described operational condition is conspicuous for those skilled in the art.
Embodiment
Simultaneous test series #1
It is invalid under the condition that this paper studied that these laboratory screenings test shows that two kinds of being considered to can be used for operation in the air/foam well are purchased corrosion inhibitor.As gas phase, technological temperature is 120 °F with air in these tests.Observing corrodibility increases and increases along with the concentration of inhibitor or whipping agent.
Except as otherwise noted, these tests are all carried out with the whirl test of describing in detail among the NACE Publication 1D 182 (Wheel Test Method).Testing liquid is specified and be purchased the preparation of one of corrosion inhibitor by the on-the-spot salt solution of 2% Repone K, specified whipping agent, air and two kinds.Test chamber is by Hastelloy C Steel structure, and each container contains two 2 1/2 inches * 1/2 inch carbon steel sample.Sample is accurately weighed before test.Each container of the about 45ml of volume is equipped with the fluid of being made up of the chemical substance of 2%KCl salt solution and specified amount, altogether 30ml.Vapour space air purge on each liquid in containers makes container be forced into the pressure of 3psig with air subsequently.Test chamber is linked to each other with wheel, and rotation is one day under 120 test temperature.
Make each test chamber be cooled to envrionment temperature then, container is opened in release.Take out sample, earlier with suppressing the corrosive pickling.Remove remaining corrosion by-products by contact the cleaning sample with steel wool pad again.Then sample is weighed, calculate erosion rate according to the difference of initial sample weight and final sample weight.Erosion rate with mils per year (mpy) report is the mean rate of used two samples in each test.
As show as shown in the I, inhibitor A, B and the whipping agent that is purchased with Homco MC-21, Homco MC-117 and Homco SF-1009 all can not suppress oxygen corrosion under test conditions respectively.The active ingredient of some inhibitor and separately the source be shown in the table X in.The two kinds of chemical substances in front are commonly used for corrosion inhibitor in the art, and a kind of chemical substance in back is in the art as whipping agent.All observing erosion rate for these chemical substances increases with chemical constitution, erosion rate viewed speed during greater than no chemical substance.Some plaques all appear in all samples.
The table I
Two kinds are purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor B 2??(wt％) | Whipping agent 3?(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11 | ????0 ????0 ????0.01 ????0.03 ????0.05 ????0 ????0 ????0 ????0 ????0 ????0 | ????0 ????0 ????0 ????0 ????0 ????0.01 ????0.03 ????0.05 ????0 ????0 ????0 | ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0.01 ????0.03 ????0.05 | ????0 ????3 ????3 ????3 ????3 ????3 ????3 ????3 ????3 ????3 ????3 | ????68 ????120 ????120 ????120 ????120 ????120 ????120 ????120 ????120 ????120 ????120 | ????24 ????24 ????24 ????24 ????24 ????24 ????24 ????24 ????24 ????24 ????24 | ????17.4 ????51.2 ????53.2 ????54.6 ????56.4 ????53.3 ????55.7 b????58.6 b????55.2 ????53.0 ????70.7 |
aUse the 30ml fluid altogether in each test.The about 45ml of system volume.Fluid is made up of the doping of 2%KCl salt solution.Vapour space air purge is forced into 3psig then, but tests except 1.
bSome plaques all appear in all samples, but these plaques are quite serious.
1Homco?MC-21
2Homco?MC-117
3Homco?SF-1009
Simultaneous test series #2
These simultaneous test proof preparations have the foamy complicacy of corrosion inhibition performance.These simultaneous tests are examined or check interaction unique between inhibitor A (Homco MC-21), inhibitor C (Homco AC-105-C) and the whipping agent (Homco SF-1009) particularly.The active ingredient of some inhibitor and separately the source be shown in the table X in.
Test with the described general step of simultaneous test series #1.Containing these the two kinds of corrosion inhibitors of prescribed concentration and the viewed erosion rate of test #4 of whipping agent is 4.77mpy.Yet, when as test #5 and #6 in the concentration of inhibitor A, C and whipping agent when increasing by 2 1/2 times and 5 times, erosion rate increases at least 3 times and 7 times respectively.When each chemical constitution is descended 50% the time by test #4, erosion rate increases nearly 15 times.Back one erosion rate with test #1 and #2 during observed similar, wherein sample does not contain inhibitor C, but contains other two kinds of chemical substances.These the results are shown in the table II.
The table II
Shown in be purchased the whirl test result of inhibitor under 120
a
| Simultaneous test number | Inhibitor A 1(wt％) | Inhibitor C 2??(wt％) | Whipping agent 3(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ??1 ??2 ??3 ??4 ??5 ??6 | ?0.10 ?0.10 ?0.01 ?0.02 ?0.05 ?0.10 | ????0 ????0 ????0.01 ????0.02 ????0.05 ????0.10 | ?0.25 ?0.25 ?0.025 ?0.050 ?0.125 ?0.250 | ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 | ????120 ????120 ????120 ????120 ????120 ????120 | ????24 ????24 ????24 ????24 ????24 ????24 | ????65.7 b????67.9 b????67.0 b????4.77 ????15.68 c????36.1 c |
aUse the 180ml fluid altogether in each test, by the 2%KCl solution composition of 10vol% kerosene and 90vol%, the chemical substance of concentration shown in wherein adding.The about 215ml of the cumulative volume of system.
bPlaque
cPlaque a little
1Homco?MC-21
2Homco?AC-105-C
3Homco?SF-1009
Simultaneous test series #3
The test-results of simultaneous test series #3 is to obtain with Corrator test method.The result is consistent with the observations that simultaneous test series #2 is reported.Be lower than and be higher than and it seems very narrow concentration range, inhibitor is all invalid under 120 °F.
Test is carried out under laboratory condition in 1 liter of erlenmeyer flask of magnetic stirring bar is housed, and test conditions is designed to simulate the corrodibility oil-water surrounding that often runs in the field work.Determine the relative efficiency of erosion rate and treatment process with Corrator Monitoring systems (Rohrback Instruments).Each test comprises is fixed in two 1 inch long carbon steel electrodes on the probe, and probe is suspended in the solution that contains inhibitor/whipping agent of stirring, and the composition of solution is shown in the table III.Technological temperature is 120 °F.
Consistent with the viewed result of simultaneous test series #2, the test #2 that contains 0.02wt% inhibitor A (HomcoMC-21), 0.02wt% inhibitor C (Homco AC-105-C) and 0.05wt% whipping agent (HomcoSF-1009) produces minimum erosion rate.Test #1, #2 that occurs in the table II of the test-results of the test #1 that occurs in the table III of simultaneous test series #3 and the serial #2 of simultaneous test and the result of #6 are similar.The active ingredient of some inhibitor and separately the source be shown in the table X in.
The table III
The result of the corrosion test series #3 that under 120, carries out with the Corrator test method
a
| Test number | Inhibitor A 1?(wt％) | Inhibitor C 2?(wt％) | Whipping agent 2?(wt％) | Temperature (°F) | Erosion rate (mpy) | |
| On average | Finally | |||||
| ??1 ??2 ??3 | ??0.10 ??0.02 ??0.10 | ???0 ???0.02 ???0.10 | ???0.25 ???0.05 ???0.25 | ???120 ???120 ???120 | ???47.3 ???6.9 ???23.9 | ???51.1 ???1.7 ???20.0 |
aTest fluid is the on-the-spot salt solution of the 2%KCl of 900ml, 100ml kerosene and the percentile additive of specified wt.Fluid under environmental stress by air saturation.Test duration 24 hours.
1Homco?MC-21
2Homco?AC-105-C
3Homco?SE-1009
Simultaneous test series #4
Test number 1-24 among the simultaneous test series #4 determines that inhibitor D (Amtech MC-1) is invalid as corrosion inhibitor under study condition.Wherein use test 25-42 proof erosion rate under test conditions of inhibitor E (Amtech B-1) relatively low.These inhibitor can be obtained by the source shown in the table X.
All tests are all carried out under 120 °F with the method shown in the front simultaneous test series #1.The test-results of this series of trials is shown in the table IV.
Table IV-part I
Shown in be purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor E 4?(wt％) | Whipping agent 3?(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ????1 ????2 ????3 ????4 ????5 ????6 | ????0 ????0 ????0 ????0 ????0.10 | ????0 ????0 ????0 ????0 ????0 | ????0 ????0 ????0 ????0 ????0.25 | ??2.4 ??2.4 ??2.4 ??2.4 ??2.4 | ?120 ?120 ?120 ?120 ?120 | ???24 ???24 ???24 ???24 ???24 | ??76.8 b??83.5 b??75.3 ??78.3 ??74.4 |
aTest(ing) liquid is 2%KCl salt solution and the 15ml kerosene of 135ml in each test, inhibitor and the whipping agent shown in wherein adding.The about 215ml of the cumulative volume of system.
bObserve serious plaque
1Homco?MC-21
2Amtech?MC-1
3Homco?SF-1009
Table IV-part II
Shown in be purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor D 2??(wt％) | Whipping agent 3?(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ??7 ??8 ??9 ??10 ??11 ??12 ??13 ??14 ??15 ??16 ??17 ??18 ??19 ??20 ??21 ??22 ??23 ??24 | ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 | ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 ???0.20 ???0.20 ???0.20 ???0.20 ???0.20 ???0.20 | ???0.20 ???0.20 ???0.20 ???0.25 ???0.25 ???0.25 ???0.20 ???0.20 ???0.20 ???0.25 ???0.25 ???0.25 ???0.20 ???0.20 ???0.20 ???0.25 ???0.25 ???0.25 | ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 | ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 | ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 | ????61.5 ????61.7 ????58.3 ????59.6 ????59.0 ????62.5 ????58.8 ????57.9 ????53.9 ????53.6 ????55.0 ????51.8 ????50.4 ????50.8 ????50.2 ????52.2 ????50.8 ????49.9 |
aTest(ing) liquid is 2%KCl salt solution and the 15ml kerosene of 135ml, inhibitor and the whipping agent shown in wherein adding.The about 215ml of the cumulative volume of system.
1Homco?MC-21
2Amtech?MC-1
3Homco?SF-1009
Table IV-part III
Shown in be purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor E 4??(wt％) | Whipping agent 3?(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ??25 ??26 ??27 ??28 ??29 ??30 ??31 ??32 ??33 ??34 ??35 ??36 ??37 ??38 ??39 ??40 ??41 ??42 | ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 | ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 ???0.20 ???0.20 ???0.20 ???0.20 ???0.20 ???0.20 | ??0.20 ??0.20 ??0.20 ??0.25 ??0.25 ??0.25 ??0.20 ??0.20 ??0.20 ??0.25 ??0.25 ??0.25 ??0.20 ??0.20 ??0.20 ??0.25 ??0.25 ??0.25 | ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 ??2.5 | ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 | ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 | ???4.99 ???5.36 ???5.06 ???4.95 ???5.88 ???4.82 ???4.86 ???4.95 ???4.29 ???3.86 ???4.67 ???4.50 ???5.02 ???4.59 ???5.09 ???5.01 ???4.55 ???4.33 |
aTest(ing) liquid is 2%KCl salt solution and the 15ml kerosene of 135ml, inhibitor and the whipping agent shown in wherein adding.The about 215ml of the cumulative volume of system.
1Homco?MC-1
2Amtech?MC-21
3Homco?SF-1009
4Amtech?B-1
Simultaneous test series #5
Simultaneous test series #5 provides the correlation data as the applicability of corrosion inhibitor under 120 about inhibitor D (Amtech MC-1), inhibitor E (AmtechB-1) and inhibitor F (Baker Cronox C-617).Test-results shows that inhibitor F (test 15) is better than inhibitor E (test 9-14), and inhibitor E obviously is better than inhibitor D (test 1-8).It is consistent that the back serial #4 of one contrast result and simultaneous test is reported.The active ingredient of some inhibitor and separately the source be shown in the table X in.
Test conditions and the results are shown in the table V in.All tests are all carried out under 120 °F in the rotation test method shown in the simultaneous test series #1 with the front.
Corrosion inhibition result according to simultaneous test series #1 to #5 has wherein assessed 6 kinds and has been purchased corrosion inhibitor, and preferred corrosion inhibitor is inhibitor F in test under these test conditionss 6 kinds.
Table V-part I
Shown in be purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor D 2??(wt％) | Whipping agent 3??(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 | ???0 ???0.10 ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.20 | ???0 ???0 ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 ???0.10 | ???0 ???0.25 ???0.20 ???0.20 ???0.20 ???0.25 ???0.25 ???0.25 | ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 ????2.5 | ?120 ?120 ?120 ?120 ?120 ?120 ?120 ?120 | ???24 ???24 ???24 ???24 ???24 ???24 ???24 ???24 | ??216.5 ??216.5 ??181.7 b??149.3 b??125.3 b??192.5 b??192.6 ??177.6 |
aTest(ing) liquid is 2%KCl salt solution and the 15ml kerosene of 135ml, inhibitor and the whipping agent shown in wherein adding.The about 215ml of the cumulative volume of system.
bSerious plaque
cSome plaques
1Homco?MC-21
2Amtech?MC-1
3Homco?SF-1009
Table V-part II
Shown in be purchased the whirl test result of inhibitor under 120
a
| Test number | Inhibitor A 1??(wt％) | Inhibitor E 4??(wt％) | Whipping agent 3??(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mph) |
| ???9 ???10 ???11 ???12 ???13 ???14 ???15 | ???0 ???0.10 ???0.15 ???0 ???0.10 ???0.15 ???0.10 | 0.10 0.10 0.10 0.10 0.10 0.10 inhibitor F 5???0.10 | ???0.20 ???0.20 ???0.20 ???0.25 ???0.25 ???0.25 ???0.25 | ???2.5 ???2.5 ???2.5 ???2.5 ???2.5 ???2.5 ???2.5 | ??120 ??120 ??120 ??120 ??120 ??120 ??120 | ???24 ???24 ???24 ???24 ???24 ???24 ???24 | ????8.88 c????10.2 c????10.4 c????9.25 c????9.78 c????9.49 ????5.49 |
aTest(ing) liquid is 2%KCl salt solution and the 15ml kerosene of 135ml, inhibitor and the whipping agent shown in wherein adding.The about 215ml of the cumulative volume of system.
bSerious plaque
cSome plaques
1Homco?MC-21
2Amtech?MC-1
3Homco?SF-1009
4Amtech B-1 (seeing note 5)
5Inhibitor F, Baker Cronox C-617
Series of trials #1
Test is all carries out under 200 °F except that one for this series of trials, determines that at last the combination of potassium hydroxide and phenol is better than the best corrosion inhibitor shown in the serial #1 to #5 of simultaneous test-be corrosion inhibitor F (Baker Cronox C-617).This series of trials determines that also potassium hydroxide/phenol corrosion inhibitor mol ratio of phenol and oxygen in testing apparatus is starkly lower than the validity under 1.0 the situation.
Similar shown in testing sequence and the simultaneous test series #1.For inhibitor F (test 4-6) and corrosion inhibitor of the present invention (test 7-12), the concentration of chemical substance, test conditions and the results are shown in shown in the VI.Proof inhibitor F 200 °F and 10 and 100psig pressure under performance can not accept (erosion rate be respectively 23.0 and 43.4mpy), and the low about order of magnitude of the erosion rate of the present invention's prescription (be respectively 2.71 and 2.73mpy).Find inhibitor F with inhibitor same concentrations of the present invention under erosion rate be the function of air pressure, and inhibitor of the present invention is not observed this dependency.As mentioned above, inhibitor of the present invention mol ratio of phenol and oxygen in system be starkly lower than 1 o'clock still effective.
The table VI
The whirl test result of the corrosion inhibition agent prescription of inhibitor F and the present invention under 120 and 200
| Test number a | Inhibitor F 1??(wt％) | ??KOH ?(wt％) | Phenol (wt%) | Whipping agent 2(wt％) | Air pressure (psig) | Temperature (°F) | Test period (hrs.) | Erosion rate (mpy) |
| ?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9 ?10 ?11 ?12 c | ????0 ????0 ????0 ????0.1 ????0.15 ????0.15 ????0 ????0 ????0 ????0 ????0 ????0 | ???0 ???0 ???0 ???0 ???0 ???0 ???5 ???10 ???10 ???10 ???10 ???10 | ???0 ???0 ???0 ???0 ???0 ???0 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 ???0.15 | ???0 ???0 ???0 ???0.25 ???0.20 ???0.20 ???0 ???0 ???0.20 ???0.20 ???0.20 ???0.20 | ????2.5 ????50 ????200 ????2.5 ????10.0 ????100.0 ????10 ????10 ????10 ????50 ????100 ????200 | ?120 ?200 ?200 ?120 ?200 ?200 ?200 ?200 ?200 ?200 ?200 ?200 | ????24 ????48 ????48 ????24 ????48 ????48 ????48 ????48 ????48 ????48 ????48 ????48 | ???216.5 b???34.0 b???102.1 b???5.49 ???23.0 ???43.4 b???5.76 ???2.78 ???2.71 ???2.82 ???2.73 ???2.19 |
aTest(ing) liquid is the 2%KCl salt solution of 80ml, wherein adds chemical substance, inhibitor and the whipping agent of going up mask body.The about 120ml of the cumulative volume of system.
bPlaque
cThe mol ratio of phenol and oxygen is 0.148 in the testing apparatus.
1Baker?Cronox?C-617
2Homco?SF-1009
Series of trials #2
This series of trials further specifies the significant inhibition corrosive nature that NaOH/ phenol and KOH/ phenol are had in high oxidation environment (air, water and carbon steel sample are at 350 and 7psig).
Test-results and condition are shown in table VII and the VIII.Identical described in testing sequence and the simultaneous test series #1.
The test-results that the institute that test #15 shows among the simultaneous test series #5 tries to be purchased most promising inhibitor F in the inhibitor is shown in to be shown in the VII.These test-results are result shown in the confirmed test series #1 under higher temperature.These results show that inhibitor F can not be as corrosion inhibitor under heating up.
The result of test #1 and #1 proves that obviously erosion rate is unacceptable in the system of being studied in the table VIII under the situation of no corrosion inhibitor.The result of test #3 and #4 shows that used whipping agent can not suppress corrosion in these research.Even test #5 gained result shows that there is the inhibition corrosion in the phenol of independent 0.30wt% also seldom.Test #6-7 and 8-9 show respectively and add NaOH or KOH causes suppressing significantly corrosion in research system.In the two, as if KOH provides better corrosion inhibition performance under given weight percent.NaOH or KOH and phenol combination unexpectedly enhancing corrosion-inhibiting prove the viewed result of various alkali metal hydroxides as test 10-15.The corrosion inhibition degree of NaOH/ phenol system (test #10-11) and KOH/ phenol system (test #12-14) is close.
Show further that 350 test-results that suppress corrosive test #17-20 down these combination of chemicals still have fabulous rejection when using with KOH and phenol under higher air pressure.The dividing potential drop of the big more corresponding oxygen oxidizer of air pressure is big more.
The table VII
Be purchased the whirl test result of inhibitor F under 300
| Test number | Inhibitor F 1???(wt％) | Whipping agent 2??(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mpy) |
| ???1 ???2 | ?????50 ?????1 | ????1 ????1 | ????7 ????7 | ???320 ???320 | ???24 ???24 | ??33.4 b??26.7 b |
aTest(ing) liquid is the on-the-spot salt solution of the 2%KCl of 80ml, component shown in the weight percent shown in wherein containing.The about 120ml of the cumulative volume of system.
bPlaque
1Baker?Cronox?C-617
2Homco?SF-1009
The table VIII
Whirl test result under 300 and 350
| Test number a | ??NaOH ?(wt％) | ??KOH ?(wt％) | Phenol (wt%) | Whipping agent 1??(wt％) | Air (psig) | Temperature (°F) | Time (hrs.) | Erosion rate (mpy) |
| ???1 ???2 ???3 ???4 ???5 ???6 ???7 ???8 ???9 ???10 ???11 ???12 ???13 ???14 ???15 ???16 ???17 ???18 ???19 ???20 | ???0 ???0 ???0 ???0 ???0 ???5 ???10 ???0 ???0 ???5 ???10 ???0 ???0 ???0 ???0 ???0 ???0 ???0 ???0 ???0 | ???0 ???0 ???0 ???0 ???0 ???0 ???0 ???5 ???10 ???0 ???0 ???5 ???10 ???10 ???1 ???1 ???5 ???10 ???1 ???10 | ??0 ??0 ??0 ??0 ??0.30 ??0 ??0 ??0 ??0 ??0.15 ??0.30 ??0.15 ??0.30 ??0.30 ??0.30 ??0.05 ??0.05 ??0.05 ??0.10 ??0.10 | ????0 ????0 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 | ???5 ???5 ???5 ???10 ???5 ???5 ???5 ???5 ???5 ???5 ???5 ???5 ???5 ???5 ???5 ???10 ???10 ???10 ???10 ???10 | ?300 ?350 ?300 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 ?350 | ???48 ???55 ???48 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 ???55 | ??11.5 b??11.6 b??13.5 b??16.4 ??14.2 b??4.06 ??6.31 ??3.70 ??3.98 ??3.11 ??2.42 ??2.44 ??2.95 ??1.90 ??3.42 b??4.27 b??3.13 ??3.32 ??3.06 ??3.43 |
aTest(ing) liquid is the 2%KCl of 80ml, component shown in the weight percent shown in wherein adding.
bPlaque
1Homco?SF-1009
Series of trials #3
This series of trials further specify phenolic compound-phenol add contain can make hydrated matrix fluid pH at least 9 contain compound K OH hydroxy or NH
4Can suppress corrosion in the time of in the salt brine solution of OH and/or whipping agent valuably.For every kind of combination, find to add phenol and reduce erosion rate (promptly improving corrosion-inhibiting).
Test-results and condition are shown in the table IX.Similar described in testing sequence and the simultaneous test series #1.The temperature that air/salt solution/sample system is exposed to 350 was tested in following 42.5 hours.Test number 1-5 relates in the brine system (test #4 and #5) of the brine system (test #3) of the brine system (test #2) of the brine system of air/contain KOH (test #1), air/contain KOH and whipping agent, air/contain KOH and phenol, air/contain KOH, whipping agent and phenol and suppresses to corrode.Test number 6-10 relates to similarly at air/contain NH
4The brine system of OH (test #6), air/contain NH
4The brine system of OH and whipping agent (test #7), air/contain NH
4The brine system of OH and phenol (test #8), air/contain NH
4Suppress corrosion in the brine system of OH, whipping agent and phenol (test #9 and #10).The concentration that the result of test #4 and #5 and test #9 and #10 also unexpectedly shows phenol erosion rate when 0.3wt% reduces to 0.15wt% reduces.As previously described, adding phenol in all tests in fluid systems all causes erosion rate to reduce.The solution ratio that contains KOH contains NH
4The order of magnitude that the solution of OH reduces is bigger.Contain NH
4The erosion rate of the comparable system of OH generally is lower than those systems that contain KOH.
The table IX
Whirl test result under 350
| Test number a,b | KOH(wt％) | NH 4OH(wt％) | Phenol (wt%) | Whipping agent c(wt％) | Erosion rate (mpy) |
| ??????1 ??????2 ??????3 ??????4 ??????5 ??????6 ??????7 ??????8 ??????9 ??????10 | ????10 ????10 ????10 ????10 ????10 ????0 ????0 ????0 ????0 ????0 | ?????0 ?????0 ?????0 ?????0 ?????0 ?????10 ?????10 ?????10 ?????10 ?????10 | ?????0 ?????0 ?????0.3 ?????0.3 ?????0.15 ?????0 ?????0 ?????0.3 ?????0.3 ?????0.15 | ???????0 ???????0.2 ???????0 ???????0.2 ???????0.2 ???????0 ???????0.2 ???????0 ???????0.2 ???????0.2 | ?????7.43 ?????7.04 ?????3.32 ?????3.20 ?????3.01 ?????4.24 ?????3.38 ?????2.81 ?????2.57 ?????2.32 |
aShared 80ml fluid in each test.The fluid of test 1-5 is by the 2%KCl prepared in saline of 80ml, wherein percentile KOH shown in the adding, phenol and whipping agent.The fluid of test 6-10 is by the 2%KCl salt solution of 65ml and the 60wt%NH of 15ml
4The OH preparation, percentile phenol and whipping agent shown in wherein adding.The cumulative volume of system is 120ml.
bTest conditions is 42.5hrs under 350 and the 7.6psig.The gas that loads is air.
cWhipping agent is Homco SF-1009.
The table X
Be purchased inhibitor
| Inhibitor | Trade(brand)name | Active ingredient 1 |
| ?????A ?????B ?????C ?????D ?????E ?????F | ????Homco?MC-21 2????Homco?MC-117 2????Homco?AC-105-C 2????Amtech?MC-1 3????Amtech?B-1 3????Baker?Cronox?C-617 4 | Amine, methyl alcohol ethylene glycol methyl alcohol ethylene glycol, methyl alcohol ethylene glycol phosphonate, butoxy ethanol |
1Disclosed component on the Material Safety Data Sheet.May there be other active ingredient but unexposed.
2Homco?International,Inc.,P.O.Box?26292,6021?Camille?Avenue,Oklahoma?City,OK,72129
3Amtech?Corp.,2221?S.Eastern,Oklahoma?City,OK,73129
4Baker?Performance?Chemicals,Inc.,3920?Esses?Lane,Houston,TX
Claims (71)
1. corrosion inhibitor, comprise at least a pH that can make water at least 9 contain compound hydroxy and at least a phenolic compound.
2. the composition of the material of claim 1, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
3. the composition of the material of claim 2, wherein said to contain compound hydroxy be alkali metal hydroxide, ammonium hydroxide or its mixture.
4. the composition of the material of claim 3, wherein said alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
5. the composition of the material of claim 4, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde, Phloroglucinol, 1,2,3-benzenetriol, 4,4-biphenol, 1,3-dihydroxy naphthlene or o-allyl phenol, or its salt.
6. the composition of the material of claim 5, wherein said phenolic compound is phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
7. the composition of the material of claim 6, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
8. the composition of the material of claim 1, wherein said corrosion inhibitor also comprises water.
9. the composition of the material of claim 7, wherein said corrosion inhibitor also comprises water.
10. aerated liquid, comprise the gas phase that is dispersed in the continuous liquid phase, wherein said liquid phase by (a) as the water of major portion and (b) corrosion inhibitor forms, it is that at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity is formed that described corrosion inhibitor is enough to make the pH of described liquid phase by at least a its concentration.
11. the composition of the material of claim 10, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
12. the composition of the material of claim 11, wherein said to contain compound hydroxy be alkali metal hydroxide, ammonium hydroxide or its mixture.
13. the composition of the material of claim 12, wherein said gas phase is made up of nitrogen and at least a component that is selected from oxygen, hydrogen sulfide or carbonic acid gas.
14. the composition of the material of claim 13, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
15. the composition of the material of claim 14, wherein said gas phase mainly is made up of air.
16. the composition of the material of claim 15, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde, Phloroglucinol, 1,2,3-benzenetriol, 4,4-biphenol, 1,3-dihydroxy naphthlene or o-allyl phenol, or its salt.
17. the composition of the material of claim 16, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
18. the composition of the material of claim 17, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
19. the aerated liquid formed by the gas phase that is dispersed in the continuous water base liquid phase as the drilling well of main in-hole fluid or in well, put in order, completion or extraction operation method, improvement is included in the described liquid phase and contains corrosion inhibitor, and described corrosion inhibitor comprises that pH that at least a its concentration is enough to make described liquid phase is at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity.
20. the method for claim 19, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
21. the method for claim 20, wherein said to contain compound hydroxy be alkali metal hydroxide or ammonium hydroxide.
22. the method for claim 21, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
23. the method for claim 22, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde or o-allyl phenol, or its salt.
24. the method for claim 22, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
25. the method for claim 24, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
26. a drilling well, completion, arrangement or reoovery method comprise:
Predetermined depth mixed gas and liquid in well, described liquid by (a) as the water of major portion and (b) corrosion inhibitor form, wherein said corrosion inhibitor comprises that pH that at least a its concentration is enough to make described liquid is at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity, suppresses the corrosive aerated liquid thereby form.
27. the method for claim 26, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
28. the method for claim 27, wherein said to contain compound hydroxy be alkali metal hydroxide or ammonium hydroxide.
29. the method for claim 28, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
30. the method for claim 29, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde or o-allyl phenol, or its salt.
31. the method for claim 29, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
32. the method for claim 31, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
33. comprise the foam of dispersed gas phase and successive liquid phase, wherein said liquid phase by (a) as water, (b) of major portion form the whipping agent of 60 to 99.75% quality foamy significant quantities and (c) corrosion inhibitor form, wherein said corrosion inhibitor is enough to make the pH of described liquid phase to form at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity by at least a its concentration.
34. the composition of the material of claim 33, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
35. the composition of the material of claim 34, wherein said to contain compound hydroxy be alkali metal hydroxide, ammonium hydroxide or its mixture.
36. the composition of the material of claim 35, wherein said gas phase is made up of nitrogen and at least a component that is selected from oxygen, hydrogen sulfide or carbonic acid gas.
37. the composition of the material of claim 36, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
38. the composition of the material of claim 37, wherein said gas phase mainly is made up of air.
39. the composition of the material of claim 38, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde, Phloroglucinol, 1,2,3-benzenetriol, 4,4-biphenol, 1,3-dihydroxy naphthlene or o-allyl phenol, or its salt.
40. the composition of the material of claim 39, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
41. the composition of the material of claim 40, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
42. the composition of claim 33, wherein said whipping agent comprise at least a N-acylsarcosine salt, N-acyl group-N-alkyl taurine sodium, alkyl sodium sulfate ester salt, ethoxylation and sulfated alcohols, ethoxylation and sulfation alkylphenol, fatty diglycollic amide, amine oxide, alkyl betaine or acyl aminopropyl trimethyl-glycine.
43. the composition of claim 33, wherein said whipping agent comprise at least a acyl aminopropyl trimethyl-glycine.
44. the composition of claim 43, wherein said whipping agent also comprise the aliphatic series or the alkylaryl sulfonated hydrocarbon of one or more following formula:
R-SO
3M
Wherein R is that the oleophilic group of 10 to 18 carbon atoms and M are arranged is basic metal or ammonium cation.
45. the composition of claim 43, wherein said whipping agent is made up of cocounut oil acyl aminopropyl trimethyl-glycine and at least a ethoxylation and sulfated alcohols.
46. at the foam formed by the gas phase that is dispersed in the continuous liquid phase as the drilling well of main in-hole fluid or in well, put in order or the well completion operations method, improvement is included in the described foam and contains corrosion inhibitor, and described corrosion inhibitor comprises that pH that at least a its concentration is enough to make described liquid phase is at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity.
47. the method for claim 46, wherein said phenolic compound is a following formula:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
48. the method for claim 47, wherein said to contain compound hydroxy be alkali metal hydroxide or ammonium hydroxide.
49. the method for claim 48, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
50. the method for claim 49, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde or o-allyl phenol, or its salt.
51. the method for claim 49, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
52. the method for claim 51, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
53. the method for claim 52, wherein said whipping agent comprise at least a acyl aminopropyl trimethyl-glycine.
54. the composition of claim 53, wherein said whipping agent also comprise the aliphatic series or the alkylaryl sulfonated hydrocarbon of one or more following formula:
R-SO
3M
Wherein R is that the oleophilic group of 10 to 18 carbon atoms and M are arranged is basic metal or ammonium cation.
55. the composition of claim 53, wherein said whipping agent is made up of cocounut oil acyl aminopropyl trimethyl-glycine and at least a ethoxylation and sulfated alcohols.
56. a drilling well, completion or adjustment method may further comprise the steps:
(a) mixed gas and liquid form foam closely, described liquid is made up of as whipping agent and (3) corrosion inhibitor that water, (2) of major portion form 60 to 99.75% quality foamy significant quantities (1), and wherein said corrosion inhibitor is enough to make the pH of described liquid phase to form at least 9 at least a phenolic compound that contains compound hydroxy and significant quantity by at least a its concentration; With
(b) in the pipe or annular space that described foam is injected into well, thereby exploit described in-hole fluid by the pipe or the annular space of non-injection.
57. the method for claim 56, wherein said phenolic compound has the following formula structure:
R wherein
1, R
2, R
3, R
4, and R
5Be independently selected from hydroxyl, contain 1 to 6 carbon atom alkoxyl group, contain alkyl, phenyl, the NO of 1 to 6 carbon atom
2, COOH, COH, sulfonic acid, the ketone that contains 1 to 6 carbon atom, F, Cl, Br, I, hydrogen or above-mentioned any acid or alcohol salt, wherein at least two above-mentioned R bases are hydrogen; Or its phenol mixture and gained compound are water dispersible or water miscible.
58. the method for claim 57, wherein said to contain compound hydroxy be alkali metal hydroxide or ammonium hydroxide.
59. the method for claim 58, wherein said alkali metal hydroxide are sodium hydroxide or potassium hydroxide.
60. the method for claim 59, wherein said phenolic compound is phenol, Ortho Cresol, adjacent fluorophenol, ortho chloro phenol, adjacent bromophenol, phenol o-iodine, o-NP, pyrocatechol, Resorcinol, methyl catechol, quinhydrones, salicylic aldehyde or o-allyl phenol, or its salt.
61. the method for claim 60, wherein said phenolic compound are phenol, Ortho Cresol, salicylic aldehyde or o-NP, or its ammonium, potassium or sodium salt.
62. the method for claim 61, wherein said phenolic compound are phenol or its sodium or sylvite and described to contain compound hydroxy be sodium hydroxide or potassium hydroxide.
63. the method for claim 52, wherein said whipping agent comprise at least a N-acylsarcosine salt, N-acyl group-N-alkyl taurine sodium, alkyl sodium sulfate ester salt, ethoxylation and sulfated alcohols, ethoxylation and sulfation alkylphenol, fatty diglycollic amide, amine oxide, alkyl betaine or acyl aminopropyl trimethyl-glycine.
64. the method for claim 56, wherein said whipping agent comprise at least a acyl aminopropyl trimethyl-glycine.
65. the method for claim 64, wherein said whipping agent also comprise the aliphatic series or the alkylaryl sulfonated hydrocarbon of one or more following formula:
R-SO
3M
Wherein R is that the oleophilic group of 10 to 18 carbon atoms and M are arranged is basic metal or ammonium cation.
66. the method for claim 64, wherein said whipping agent is made up of cocounut oil acyl aminopropyl trimethyl-glycine and at least a ethoxylation and sulfated alcohols.
67. the method for claim 62, wherein said whipping agent comprise at least a acyl aminopropyl trimethyl-glycine.
68. the method for claim 67, wherein said whipping agent also comprise the aliphatic series or the alkylaryl sulfonated hydrocarbon of one or more following formula:
R-SO
3M
Wherein R is that the oleophilic group of 10 to 18 carbon atoms and M are arranged is basic metal or ammonium cation.
69. the method for claim 67, wherein said whipping agent is made up of cocounut oil acyl aminopropyl trimethyl-glycine and at least a ethoxylation and sulfated alcohols.
70. the method for claim 56, wherein said foam are exposed under 200 the temperature at least.
71. the method for claim 56, wherein said foam are exposed under 350 the temperature at least.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180471 CN1234821A (en) | 1996-10-15 | 1996-10-15 | Corrosion inhibitor for wellbore application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180471 CN1234821A (en) | 1996-10-15 | 1996-10-15 | Corrosion inhibitor for wellbore application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1234821A true CN1234821A (en) | 1999-11-10 |
Family
ID=5127909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96180471 Pending CN1234821A (en) | 1996-10-15 | 1996-10-15 | Corrosion inhibitor for wellbore application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234821A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497743A (en) * | 2013-09-18 | 2014-01-08 | 新疆贝肯能源工程股份有限公司 | Artificial oil-based drilling fluid strong inhibitor for drilling fluid and preparation method of inhibitor |
| CN107949609A (en) * | 2015-09-03 | 2018-04-20 | Ppg工业俄亥俄公司 | Corrosion inhibitor and the coating composition containing it |
-
1996
- 1996-10-15 CN CN 96180471 patent/CN1234821A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497743A (en) * | 2013-09-18 | 2014-01-08 | 新疆贝肯能源工程股份有限公司 | Artificial oil-based drilling fluid strong inhibitor for drilling fluid and preparation method of inhibitor |
| CN103497743B (en) * | 2013-09-18 | 2016-08-10 | 新疆贝肯能源工程股份有限公司 | Drilling fluid imitative oil base drilling fluid potent inhibitor and preparation method thereof |
| CN107949609A (en) * | 2015-09-03 | 2018-04-20 | Ppg工业俄亥俄公司 | Corrosion inhibitor and the coating composition containing it |
| US10619056B2 (en) | 2015-09-03 | 2020-04-14 | Ppg Industries Ohio, Inc. | Corrosion inhibitors and coating compositions containing the same |
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