CN100538002C - Use different scale inhibitors to make the method for oilfield stimulation - Google Patents
Use different scale inhibitors to make the method for oilfield stimulation Download PDFInfo
- Publication number
- CN100538002C CN100538002C CNB2004800245484A CN200480024548A CN100538002C CN 100538002 C CN100538002 C CN 100538002C CN B2004800245484 A CNB2004800245484 A CN B2004800245484A CN 200480024548 A CN200480024548 A CN 200480024548A CN 100538002 C CN100538002 C CN 100538002C
- Authority
- CN
- China
- Prior art keywords
- group
- different
- scale inhibitor
- fluid
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to make the method for oilfield stimulation, comprise that the inflow stream with a kind of fluid injects the Petroleum Production well that is connected with the oil field, replace described oil, and reclaim the outflow logistics of the fluid that comprises described oil, wherein, at least two logistics are injected at least two production areas of an oil well, perhaps inject at least two different Petroleum Production wells, to flow out logistics from described two districts or well at least two before reclaiming merges, but the scale inhibitor that wherein will have the test section is introduced described oil field and/or described fluid, it is characterized in that, use two kinds of different scale inhibitors, be used for described two districts or well, but described different scale inhibitor has different test sections, but these different test sections can be distinguished by analyzing.
Description
Technical field
The present invention relates to make the method for oilfield stimulation, it comprises the use scale inhibitor.
Background technology
In oil recovery, more importantly in secondary oil recovery (wherein in order to replace crude oil, fluid, preferred water-based fluid being injected in the oil well), the formation of incrustation scale may cause that the hole in pipeline and the oil-bearing layer stops up, and therefore reduces or even stops flowing of oil.Therefore, incrustation scale has reduced the oil recovery productive rate.
Form in order to overcome incrustation scale, it is known using incrustation scale to suppress polymer.The processing horizontal of the highest hundreds of part/1,000,000 parts (ppm) is normally effective.Usually incrustation scale is suppressed the polymer adding and want processed fluid, perhaps can be applied in the oil bearing bed by means of " squeeze treatment ".Squeeze treatment comprises scale inhibitor is pumped into the oil exploitation well that inhibitor enters formation rock and is retained in the there like this.When described well put into production again, the fluid of output was handled by the scale inhibitor that leaches from formation rock.Therefore scale inhibitor is released in the fluid.Can be applied to scale inhibitor moisture or non-aqueous media in.Purpose is to prevent from or be controlled in the system of using described fluid to form incrustation scale.
Have only when the scale inhibitor polymer exists with the processing horizontal in the effective range of the regulation that is in product, for example the minimum inhibitor concentration (MIC) with specific system (water+scale inhibitor) exists, and the formation of incrustation scale could be controlled.At production period, (for example owing to be consumed) needs squeeze note again when inhibitor is released.Utilize squeeze treatment, the scale inhibitor concentration in the produced fluid will reduce along with the past of time, carry out " squeeze note again " operation of repetition up to needs.In addition, scale inhibitor may lose by for example absorption or degraded.Therefore, in order to remedy this loss, need the supplementing water scale inhibitors.The result of fouling is normally serious in this application, and it is topmost therefore avoiding fouling.Total says, can find out, the concentration of scale inhibitor is extremely important in the fluid of handling, and the chemical analysis of incrustation scale control polymer is difficult in the ppm level always.
Recently, the problem of analyzing in offshore oil field becomes more outstanding because the several single well in subsea-completed well on the seabed united, and the fluid that merges by pipeline be transported to nearest may be at the production platforms beyond tens miles.In such form,, can not determine which specific well has too many incrustation scale, and/or determine in which well, should add scale inhibitor if oil yield reduces in the fluid of the merging of reclaiming.Therefore, must stop the production of all wells sometimes, perhaps add much more scale inhibitor (for example in the well of the less scale inhibitor of needs, adding a large amount of scale inhibitors).This has just reduced total productive rate, and/or is not that cost is effective.
Summary of the invention
The invention solves above-mentioned problem.Therefore, the present invention relates to make the method for oilfield stimulation, comprise that the inflow stream with a kind of fluid injects the Petroleum Production well that is connected with the oil field, replace described oil, and reclaim the outflow logistics of the fluid that comprises described oil, wherein, at least two logistics are injected at least two production areas of an oil well, perhaps inject at least two different Petroleum Production wells, to flow out logistics from described two districts or well at least two before reclaiming merges, but the scale inhibitor that wherein will have the test section is introduced described oil field and/or described fluid, it is characterized in that, use two kinds of different scale inhibitors, be used for described two districts or well, but described different scale inhibitor has different test sections, but these different test sections can be distinguished by analyzing.These operations also are called as a kind of production method.
Usually, the amount of the different scale inhibitors in the fluid that described method also comprises mensuration and reclaimed or from the amount of a kind of fluid of wherein obtaining, if and the amount of scale inhibitor is lower than set-point, the normally minimum inhibitor concentration of this set-point then solves the incrustation scale that occurs and forms problem in district that uses described scale inhibitor or well.
The different incrustation scale that the invention still further relates to the novelty that can be used for implementing said method suppresses polymer.
The specific embodiment
Definition
Polymer is meant the macromolecular chain that comprises repetitive.Copolymer is meant the polymer that comprises repetitive and have at least two kinds of different unit.Copolymer comprises the polymer with two kinds of different repetitives, the polymer (being sometimes referred to as ter-polymers) with three kinds of different repetitives or the polymer with more kinds of repetitives.
" MIC " refers to minimum inhibitor concentration.MIC can be according to NACS standard TM0197-97, the laboratory screening test, entry number 21228, NACE International, 1997, a middle static bottle examination method of describing is estimated, and wherein measures scale inhibitor prevents that barium sulfate and/or strontium sulfate are precipitated out from solution ability (for the oil and natural gas production system).
The icp analysis method refers to the inductively coupled plasma analytical method.This analytical method is known for the those skilled in the art of detection, evaluation and/or quantitative single chemical element.
The use of oil recovery process and scale inhibitor
It is well known by persons skilled in the art making the method for oilfield stimulation by the injection fluid.Described method includes, but are not limited to, and is called as the method for " water filling ".
Water filling is a normally used technology in the oil-recovery operations.Water is injected into the formation water storage by injecting well under pressure; This process drives oil and enters producing well by mineral deposit and rock stratum.In the outflow logistics that comprises water and oil, reclaim the oil of displacement then.That in off-shore operation, be easy to obtain and comprise a large amount of dissolved saltses, for example sulfate as the seawater of the injection water in the water flood operations usually.The interaction of injecting the formation water in water (not having under the situation of effective scale inhibitor) and described storage will produce undesirable inorganic deposition (mainly being the dirty salt of causing of calcium sulfate, barium sulfate and strontium sulfate), and it finally stops up pipe, valve and the pump of oil recovery process equipment.The additional conditions of deposition that aggravation causes dirty salt are included in barium, strontium, calcium or the iron ion of the pressure, high temperature and the high concentration that exist in the typical oil-recovery operations.
In order to solve the problem that forms incrustation scale, can use " squeeze note " technology.Usually, at first well is washed in advance with seawater, randomly,, comprise the injecting step of scale inhibitor then so that regulate rock with for example surfactant processing of preposition compound; Succeeded by adding additional seawater (flushing (over flush) step at last), so that scale inhibitor further is distributed in the described storage, to be adsorbed in mineral deposit and the rock stratum (matrix of underground petroleum-containing formation).During squeeze treatment, oil-recovery operations is interrupted.When oil producing operation restarts, the scale inhibitor of absorption will discharge (desorption or dissolving) lentamente from the matrix of stratum, and prevent to cause dirty salt precipitate during oil-recovery operations subsequently.For being the oil field of feature with " badly " condition (for example high barium level or low pH), the typical time before the other squeeze treatment of needs is 1 to 6 months; The squeeze note life-span of wishing is 6 to 24 months, preferred 12 to 24 months or longer.Condition is abominable more, forms the metal sulfate dirt and stops up subsequently and to silt the tendency of oil field matrix and Petroleum Production equipment up big more.
In order to solve the problem that forms incrustation scale, scale inhibitor directly can also be added and inject fluid (normally water-based fluid, preferably seawater base fluid).
Useful technology also comprises by the minor diameter tubing string and applies or place in the rat hole (rat hole) of well.
If used squeeze treatment, the fluid that then comprises incrustation scale inhibition polymer is construed as forcing incrustation scale to suppress the fluid that polymer enters well or formation rock, and perhaps described incrustation scale suppresses the fluid that polymer has discharged therein.
The down-hole chemical configuration is conventional, and can be undertaken by squeeze treatment effectively, and it can protect the stratum of about 20 feet radius of production well bore and near the periphery of wellhole simultaneously.This batch technique is included in and pumps into chemicals under the producing well and end Petroleum Production when entering the stratum, closes described well and interacts to allow chemicals and formation rock, restarts production then.Described chemicals discharges from rock lentamente, gets back to the face of land with produced fluid.Pre-good antiscale property requires the inhibitor level in the produced fluid to be higher than MIC.Inhibitor in high level arrives under the absorption on stratum, observes slowly under lower concentration and returns (for the MIC that requires, must optimize absorption).These return the produced fluid of having protected larger volume, have prolonged the squeeze note life-span.When being on close level MIC, the inhibitor in the produced fluid repeats squeeze note.
The main purpose of " mark " polymer inhibitor is to prevent fouling in the seabed comprehensive development of extensive investment.Yet the cost of squeeze treatment is huge in these wells, and main cause is to incur loss through delay to recover the oil and access charge.By contrast, inhibitor chemicals cost is less.Therefore, the measure (owing to preferably the inhibitor of different wells being analyzed) at interval of the squeeze note in these wells of any minimizing all can be saved cost undoubtedly.In addition, several functional groups can promote the absorption to formation rock, and infer that the auxiliaring effect that comprises hydrophobicity " mark " in polymer is the stratum absorption that can improve inhibitor.
The Main Stage of squeeze note operation comprised with the next stage:
(i) pre-flushing: this is made up of the dilute solution of inhibitor in seawater, and it comprises surfactant or demulsifying agent usually.Therefore it reduce near the absorption of wellhole in order to the cooling stratum, and promote that inhibitor further enters the stratum.What have no less important is the displacement of formation water and the formation of buffer area, to avoid incompatibility any and the high concentration inhibitor that injects, particularly all the more so when relating to high salinity/high-calcium ionic formation water.Described pre-flushing can also be removed residual face of land oil, to improve wettability.
(ii) inhibitor injects: main inhibitor inorganic agent is normally at the 5-10% of seawater activity inhibitor.With maximum inhibitor Adsorption Modelization (according to isotherm, annotate (corefloods) or obtain by historical matching method more accurately by core) and the superficial area modelling that will can be used for adsorbing, best inhibitor concentration and volume have been determined, so that make the squeeze note lifetime, and do not inject superfluous chemicals.
(iii) flushing at last: the major part of injecting fluid volume in this stage.Described fluid is used to inhibitor liquid plug further is flushed in the stratum, reaches 8 to 15 feet radial distance.This increased the inhibitor contact rock superficial area and improved adsorption levels.This also replaces inhibitor the stratum of the heat that can carry out bigger absorption near the wellhole of cooling.With the volume-based modelization of injecting, make obtaining balance to restarting to produce the possibility that prolongs the squeeze note life-span under the needs with raising and change the stratum wetability.Also have such danger, if promptly inject too far in the stratum, then inhibitor will return with the level that is lower than MIC.
(iv) " close ": well is shelved, be adsorbed onto on the rock to allow inhibitor.Normally 6 to 12 hours closed-in time, depend on that inhibitor absorption reaches the needed time span of balance.Under higher temperature, the rate of adsorption is higher, so the shut-in time can reduce.Modelling makes the inhibitor level of absorption and delay cost for oil production obtain balance.
(iv) back production: restart to produce with initial flow direction.Inhibitor is desorption from formation rock, and gets back to the face of land in produced fluid.
In the method for the invention, there are at least two production areas or at least two oil-producing wells to be simulated simultaneously or use.Therefore, at least two fluid streams are injected in the described production area, perhaps are injected in the described oil-producing well.Two outflow logistics that comprise oil have been obtained.Described two logistics are merged, and obtain the single recovery fluid stream of oil-containing.The merging of flowing out logistics is carried out in the seabed usually, and described single recovery logistics is piped to production equipment, for example production platform usually.This form wherein flows out logistics and is merged, and has simplified operation and/or actual many wells or zone that allow and/or the effective number of cost are increased production.Use scale inhibitor as described above, can carry out, promptly before volume increase, described inhibitor is injected or introducing oil field (at different production areas or well), perhaps undertaken by directly joining in the fluid according to squeeze treatment.
According to the present invention, used different scale inhibitors, described different scale inhibitor is used to different zones or well.But different scale inhibitors has different test sections, and it can be distinguished by analyzing.Described different part is also referred to as mark.Because described different part, described scale inhibitor is different.In different scale inhibitors, other groups, part or unit can be identical.In other words, the difference between the different scale inhibitor can only be made up of described detectable part or mark.
But use has the different scale inhibitor of different test sections, the amount of the described scale inhibitor in the feasible recovery fluid that can be combined is analyzed, therefore, because scale inhibitor is used to a certain district or well, so can determine to have the specific district or the well of too many incrustation scale, and/or determine wherein should introduce the district or the well of scale inhibitor.This introducing of scale inhibitor can be implemented by scale inhibitor being added specific fluid, perhaps by described district or well are carried out squeeze note or again squeeze note implement.Avoided like this scale inhibitor is added in unwanted district or the well, and/or for all districts or well are carried out squeeze note again and stop the production of all districts or well simultaneously.
Therefore, method of the present invention generally includes the amount of the different scale inhibitors in the fluid that mensuration reclaims or from the amount of a kind of fluid of wherein obtaining, if and the amount of scale inhibitor is lower than set-point, for example MIC then solves the incrustation scale that occurs and forms problem in district that uses described scale inhibitor or well.In brief, by being introduced, the scale inhibitor of special use is used for the specific district or the fluid of well with incrustation scale problem, perhaps by more special-purpose scale inhibitor is introduced described fluid, perhaps according to squeeze treatment technology by the scale inhibitor of special use is introduced the specific oil field with incrustation scale problem, solve the incrustation scale problem.The introducing of special-purpose scale inhibitor is preferably carried out under the situation that other districts or well do not stop to produce.
For example, described scale inhibitor is introduced water-based fluid, or more scale inhibitor is introduced described fluid, perhaps scale inhibitor is introduced described oil field according to squeeze treatment.
According to first embodiment of the present invention,, for example periodically, continuously, constantly or when needed, be incorporated in the described fluid according to analysis with scale inhibitor.More properly, scale inhibitor is incorporated into is used for wherein using the described district of this scale inhibitor or the fluid of well.According to the analysis that the recovery fluid that is combined carries out, consumption and frequency can change.
According to second embodiment of the present invention, before volume increase (promptly before replacing crude oil effectively), different scale inhibitor is introduced the oil field, and this implements by force different described inhibitor to enter described oil field (enter different districts or by different wells) according to squeeze treatment.More properly, for the district or the well that use described scale inhibitor, force (perhaps making) scale inhibitor to enter different districts or by different wells by squeeze note.For different districts or well, the frequency of squeeze note (perhaps squeeze note) again operation can change according to the analysis that the recovery fluid that is combined carries out.The squeeze note process certainly comprises any other the step that can be used for such process, for example with the described district of the pre-flushing of seawater.Squeeze note operation and preparation are that the oil recovery those skilled in the art are known.
To the quantitative analysis of scale inhibitors different in the fluid that reclaims or measure and to be suitable for detecting described different part or the method for mark is carried out by any.In preferred embodiments, all scale inhibitors can be distinguished by single analytical method.According to this embodiment, measure the step of the amount of different scale inhibitors and use single equipment to carry out.
Analytical method depends on detectable part.The analytical method that is fit to comprises induces coupled plasma, fluorometry and colorimetric method.For some preferred part, and scale inhibitor, some preferable methods is described below.
Scale inhibitor
Different scale inhibitors is to have the different detectable parts (mark) and the compound of randomly same or different other groups, part or unit.Preferred scale inhibitor is to have the incrustation scale inhibition polymer that incrustation scale suppresses the mark of unit and indexing unit.
But the example of preferred different test section comprises and is selected from following part:
A) atom mark part comprises that at least one is selected from the atom of boron, silicon and germanium,
B) derived from acetoxyl group-styrene, preferred 4-acetoxyl group-styrene or derived from the part of o-allyl phenol.
C) derived from the part of monomer with following general formula:
X
2C＝CYY’，
Wherein:
-X is same or different, is hydrogen atom or C
1-C
4Alkyl group,
-Y is hydrogen atom or C
1-C
4Alkyl group,
-Y ' is the group with general formula-L-Arom, wherein
-L is covalency keyed jointing or the organic linking group of divalence, and it randomly comprises hetero atom, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic rings, and described ring comprises the carbon atom of conjugation and randomly nitrogen or oxygen atom, and the hydrogen atom or the substituting group that are connected to described carbon atom,
D) pass through the unit of derived from ethylene base benzyl chloride and the part that following substance reaction obtains after the polymerization:
The amino pyrene-1,3 of-8-, the 6-trisulfonic acid, perhaps
-9-(2-(carbethoxyl group) phenyl)-3, two (ethylamino-)-2 of 6-, 7-dimethyl xanthene chloride (rhodamine 6G), perhaps
The blue CMAC of-CellTracker,
Perhaps its salt,
E) derived from by the amino pyrene-1,3 of vinyl chloride and 8-, the part of the monomer that 6-trisulfonic acid or its reactant salt obtain,
F) comprise the part of at least one phosphate or phosphonate groups,
G) comprise the part of at least one sulfonate or sulfonic acid group.
As the part of the unit of polymer, be provided in following about the more details of these parts.
The example of operable different scale inhibitors is included in the scale inhibitor of describing in the following document, is incorporated herein these documents as a reference:
GB2152937；WO2001007430；WO98/02492；US5,808,103；US6,312,644；US5,171,450；US5,043,406；US4,999,456；US4,813,973；WO2001081654；US5,986,030；WO2001007430；US4,194,877；EP647,598；US5,378,784；US6,077,461；WO00/53235；US6,218,491；US5,171,450；US5,260,386；US5,216,086；US5,128,419；US4,813,973；EP657,474；US6,040,406；WO9735192；EP0,613,863；US5,389,548；US4,894,346；EP861846.
Useful incrustation scale suppresses polymer, poly-aspartate ester polymer, polyvinylsulfonic acid ester polymer or copolymer, the polyacrylic acid based polyalcohol that polymer also comprises the phosphorus end-blocking.
Other examples of operable scale inhibitor are included in the scale inhibitor of describing in the document WO 03/029153, and the document is incorporated herein by reference.These scale inhibitors comprise can be by the phosphonate moiety of I.C.P detection.Therefore, one of described different scale inhibitor can be a kind of like this polymer, it has phosphate moiety at least, forms by being selected from following monomer: at least a olefinic unsaturated (two) carboxylic acid monomer, at least a olefinic unsaturated ethylene sulfonate monomer with and composition thereof.
The incrustation scale of mark suppresses copolymer
The incrustation scale that all or some described different scale inhibitors advantageously comprise the mark of at least two kinds of different units suppresses polymer: incrustation scale suppresses unit and indexing unit.Because described polymer comprises these two kinds of different unit at least, therefore described polymer is also referred to as copolymer.Incrustation scale suppresses the formation that the unit prevents incrustation scale.Indexing unit can detect by analytical method.Do not get rid of the situation that indexing unit prevents that equally incrustation scale from forming.Not getting rid of incrustation scale inhibition unit is detectable situation.
Described polymer prepares by monomer polymerization, randomly make the polymer and the reaction of a kind of compound that obtain then, with by chemical method with several object element modifications at least, these object elements are to form the possibility of covalent bond with the compound of described introducing and combined because have.This further being reflected at is hereinafter referred to as the polymerization afterreaction.Usually carrying out the polymerization afterreaction comes modification will constitute the unit of the polymer of indexing unit.
Any polymerization all can be used for making described polymer.Free radical polymerisation process is preferred.The method that is fit to comprises water base body/dispersin polymerization, polymerisation in solution or emulsion polymerisation.Preferred polymerization process is polymerisation in solution.According to the method, the water adding is equipped with the reaction vessel of mechanical agitator and water condenser, and is heated to 90 ℃.Can perhaps can add afterwards to wherein adding polymerization initiator.Described " mark " monomer also be introduced in this material, joins in the polymer feed, perhaps charging respectively.In 6 hours, with monomer feed, soluble initiator feed and randomly the chain-transferring agent charging add described container.The level of using suitable salt to neutralize and require after the polymerization.These technologies and method are well known by persons skilled in the art.
Novel incrustation scale suppresses polymer
It is to comprise the incrustation scale that incrustation scale suppresses unit and indexing unit to suppress polymer that the incrustation scale that can be used for implementing the novelty of described method suppresses polymer, and wherein indexing unit is selected from lower unit:
A) atom indexing unit comprises that at least one is selected from the atom of boron, silicon and germanium,
B) derived from acetoxyl group-styrene, preferred 4-acetoxyl group-styrene or derived from the unit of o-allyl phenol,
C) derived from the unit of monomer with following general formula:
X
2C＝CYY’，
Wherein:
-X is same or different, is hydrogen atom or C
1-C
4Alkyl group,
-Y is hydrogen atom or C
1-C
4Alkyl group,
-Y ' is the group with general formula-L-Arom, wherein
-L is covalency keyed jointing or the organic linking group of divalence, and it randomly comprises hetero atom, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic rings, and described ring comprises the carbon atom of conjugation and randomly nitrogen or oxygen atom, and the hydrogen atom or the substituting group that are connected to described carbon atom,
D) pass through the unit of derived from ethylene base benzyl chloride and the unit that following substance reaction obtains after the polymerization:
The amino pyrene-1,3 of-8-, the 6-trisulfonic acid,
-9-(2-(carbethoxyl group) phenyl)-3, two (ethylamino-)-2 of 6-, 7-dimethyl xanthene chloride (rhodamine 6G), perhaps
The blue CMAC of-CellTracker,
Perhaps its salt and
E) derived from by the amino pyrene-1,3 of vinyl chloride and 8-, the unit of the monomer of 6-trisulfonic acid or the preparation of its reactant salt.
A) in one embodiment, the indexing unit of copolymer is the atom indexing unit, comprises at least a atom that is selected from boron, silicon and germanium.These unit can by any method that is suitable for detecting boron, silicon or germanium atom for example ICP detect.Boron can also be by it with carminic acid reaction and by photometer detection (0-14mg/l).(0-1 6mg/l) also can be detected in the mode identical with phosphorus, and wherein the blue reaction of itself and molybdate provides silicomolybdic acid, and silicomolybdic acid can be reduced by amino acid, provides the navy blue that is directly proportional with silica concentration for low dioxide-containing silica.List of references about these two kinds of analytical technologies is a HACH water analysis handbook).
Any unit that comprises above-mentioned atom all can be used as indexing unit.Described unit can be derived from the monomer that comprised described atom before polymerization.Described unit further according to polymerization after scheme, obtain by preceding body unit and the compound reaction that comprises described atom.
A1) example of atom indexing unit comprises the unit that comprises borate (boronate) or boron group, for example:
A1.1) derived from following unit: 4-vinyl-benzyl-boric acid (boronic acid) or 4-vinyl-benzyl-borate (VBB), acryloyl group phenyl boric acid or acryloyl group phenyl boric acid salt, methacryl phenyl boric acid or methacryl phenyl boric acid salt, 3-acrylamide phenyl (aclylamodiphenyl) boric acid or 3-acrylamide phenylboronate, 3-Methacrylamide phenylboric acid or 3-Methacrylamide phenylboronate
Vinyl benzyl borate (VBB)/
4-vinyl benzene ylboronic acid
A1.2) unit and the BBr by comprising the trimethyl silane group after the polymerization
3Reaction and the unit that randomly further reacts acquisition with alcohol.
A2) example of atom indexing unit also comprises after the polymerization by derived from the unit of glycerin monomethyl acrylic ester and the compound that the comprises boron unit that obtains of boric acid or boric acid (boronic acid) reaction (hydroboration) for example.
Glycerin monomethyl acrylic ester (GMMA)
A3) example of atom indexing unit also comprises pi-allyl triethyl group germanium,
Pi-allyl triethyl group germane (ATEG)
A4) example of atom indexing unit also comprises vinyl trialkyl silane, for example vinyl trimethylsilane.
Vinyl trimethylsilane (VTMS)
B) in another embodiment, the indexing unit of described copolymer is derived from the unit of acetoxyl group-styrene, preferred 4-acetoxyl group-styrene (selective hydrolysis), perhaps derived from the unit of o-allyl phenol (it is the alcohol with diazo reaction).Detect reagent for example behind the diazol being exposed to, these unit can be by any suitable method detection, for example colorimetric method.The color intensity that is produced by product can use the ultraviolet spectrophotometric determination.The diazol that is fit to is a p-nitrophenyl diazonium hexafluorophosphate.Can think, according to Beer-Lambert law, color intensity relevant with reaction product concentration (reaction product concentration is equivalent to polymer concentration).By with the color intensity of polymer samples and the calibration curve contrast that obtains from polymer samples, determined polymer concentration with concentration known.
For reaction can be carried out, must be by making 4-acetoxyl group-cinnamic hydrolysis of ester group be alcohol the solution boiling.Absorbance can be measured under 500 nanometers.Following scheme is to use the example of o-allyl phenol:
C) in another embodiment, the indexing unit of copolymer is the unit derived units derived from the monomer with following general formula:
X
2C＝CYY’，
Wherein:
-X is same or different, is hydrogen atom or C
1-C
4Alkyl group,
-Y is hydrogen atom or C
1-C
4Alkyl group,
-Y ' is the group with general formula-L-Arom, wherein
-L is covalency keyed jointing or the organic linking group of divalence, and it randomly comprises hetero atom, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic rings, and described ring comprises the carbon atom of conjugation and randomly nitrogen or oxygen atom, and the hydrogen atom or the substituting group that are connected to described carbon atom.
Arom preferably has the group of at least 10 conjugation carbon atoms, preferred at least 14 carbon atoms at least three conjugation aromatic rings.The conjugation aromatic rings is C preferably
5Perhaps C
6Ring.Arom advantageously has the group of naphthalene, anthracene, pyrene or luxuriant and rich with fragrance part, and described part randomly has substituting group.
L is covalency keyed jointing or divalence C preferably
1-C
12Alkyl group, perhaps have general formula-O-,-CO-O-, CO-NH-or-group of O-CO-.
Particularly preferred indexing unit is derived from ethylene base anthracene, preferably derived from the unit of 9-vinyl anthracene.
9-vinyl anthracene (9-VA)
Preferably, described different scale inhibitor at least a is that the incrustation scale that comprises derived from the mark of the indexing unit of 9-vinyl anthracene suppresses polymer.
Other unit comprise derived from following unit: α-vinyl naphthalene, 1-vinylpyrene, 4-vinyl-9,10-diphenylanthrancene, 3-vinyl phenanthrene, 9-vinyl acridine.
These unit can detect by any suitable method, and for example fluorometry is for example used the fixed wave length fluorescence photometer.Usually, detection is carried out under polymer maximum excitation (ex) and emission (em) wavelength.These can use scanning fluorimeter to measure under scanning mode.Can think that fluorescence level is determined by Beer-Lambert law.Therefore, by with the emissive porwer of polymer samples and the calibration curve contrast that obtains from polymer samples, can determine polymer concentration with concentration known.
D) in another embodiment, indexing unit is by the unit of derived from ethylene base-benzyl chloride after the polymerization and the unit of following substance reaction acquisition:
The amino pyrene-1,3 of-8-, the 6-trisulfonic acid, perhaps
-9-(2-(carbethoxyl group) phenyl)-3, two (ethylamino-)-2 of 6-, 7-dimethyl xanthene chloride (rhodamine 6G), perhaps
The blue CMAC of-CellTracker,
Perhaps its salt.
Vinyl chloride (VBC) rhodamine 6G
The amino pyrene-1,3 of 8-, 6-trisulfonic acid (APTS)
These unit can use scanning fluorimeter to measure under scanning mode.Can think that fluorescence level is determined by Beer-Lambert law.Therefore, by with the emissive porwer of polymer samples and the calibration curve contrast that obtains from polymer samples, can determine polymer concentration with concentration known.The example of numerical value below is provided, has limited the scope of the invention but be not used in.
| Copolymer | Excitation wavelength (nm) | Emission wavelength (nm) |
| AA ＊/ 0.01 mole of % rhodamine 6G | 520 | 550 |
| AA ＊/ 0.1 mole of % rhodamine 6G | 520 | 550 |
| AA ＊-0.1 mole of %9-vinyl anthracene copolymer | 260 | 410 |
| AA ＊-0.05 mole of %9-vinyl anthracene copolymer | 260 | 410 |
| AA ＊-0.01 mole of %9-vinyl anthracene copolymer | 300 | 380 |
*Acrylic acid
F) in another embodiment, described indexing unit is the unit that comprises at least one phosphate or phosphonate groups, for example derived from the unit of phosphate (methyl) acrylate and (methyl) allyl hydroxyl phosphate.These unit can detect by any suitable method, for example ICP.
G) in another embodiment, described indexing unit is the unit that comprises at least one sulfonate or sulfonic acid group, for example styrene sulfonate and styrene sulfonic acid.These unit can detect by any suitable method, and for example colorimetric method is for example measured the ultraviolet spectrum under the absorbance of maximum.Can think that color intensity is relevant with polymer concentration according to Beer-Lambert law.By with the color intensity of polymer samples and the calibration curve contrast that obtains from polymer samples, determined polymer concentration with concentration known.These analyses are well known by persons skilled in the art.
SSS (NaSS)/
The 4-vinylbenzenesulfonic acid
Incrustation scale suppresses the unit
Incrustation scale suppresses the unit and is preferably selected from:
-vinyl sulfonic acid, perhaps vinylsulfonate,
-vinyl phosphonate, perhaps vinyl phosphonic hydrochlorate,
-EDP, perhaps its salt,
-acrylic acid,
-methacrylic acid,
-vinylacetate,
-vinyl alcohol,
-unsaturated list or omega-dicarboxylic acids or acid anhydrides, for example maleic anhydride, maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, crotonic acid, iso-crotonic acid, angelic acid, tiglic acid,
-vinyl chloride,
-styrene-p-sulfonic acid, perhaps styrene sulfonate,
-acrylamido-2-methyl propane sulfonic acid (AMPS),
-HPAA (HPA),
-hypophosphorous acid class, for example H
3PO
3, provide general formula-PO (OH)-the unit,
-acrylamide,
-have a general formula HC ≡ C-CH
2The propargyl alcohol of-OH,
-butyr-1, the 4-glycol and
-its mixture.
The monomer (for example HPA or vinyl alcohol) of allegedly introducing hydroxyl can help to be adsorbed onto on the barium sulfate crystal, alcohol groups has the good absorption to the active growth of crystallization position, with its sealing, can be used for high calcium salt solution effectively, it makes other acidic functionality inactivations.The monomer of introducing amine groups can help to be adsorbed onto calcium carbonate crystal.Other sulfonated monomers (for example AMPS or vinyl sulfonic acid or sulfonate) can improve the salt water-compatible.
Other unit (other functions)
Though said units is generally comprised within the main polymer chain, can should be mentioned that described copolymer can comprise other unit and/or other groups.Other groups comprise the group that is connected at least one polymer ends.These groups can be produced by polymerization initiator, perhaps can be the end-capped groups.They can not have specific function, perhaps can constitute incrustation scale and suppress group, labelling groups or favourable group or other groups in the described inhibitor of preparation.
Therefore, other groups or unit comprise having general formula X "
2O
3P-CHY " CZ "
2PO
2X "-group or unit, X wherein " be H or alkali metal, alkaline-earth metal or other polyvalent metals, ammonium or organic base, group, Y " and each Z ", can be same or different, each is hydrogen, PO naturally
3X
2, SO
3X or CO
2X group or alkyl or aryl moiety.Example is derived from ethylene base phosphoric acid (VPA) or ethenylidene-1, the unit of the addition product of 1-di 2 ethylhexyl phosphonic acid (VDPA) and hypophosphorous acid or its salt.This class group or unit are described in the document EP 861846.Group or unit that other are possible are described among the GB1458235.These other groups or unit can help to detect described polymer, and/or help the incrustation scale inhibitory action.
Styrene sulfonic acid, styrene sulfonate, 4-vinylbenzenesulfonic acid or 4-vinylbenzenesulfonic acid salt in so-called squeeze treatment, especially at high temperature and/or under the high pressure, can help to control the desorption that incrustation scale suppresses polymer.
Molecular weight data and other parameters
Polymer of the present invention preferably has 500 to 20000 gram/moles, the more preferably weight average molecular weight of 1000 to 8000 gram/moles.The weight average molecular weight of polymer or copolymer can be passed through SEC/gel permeation chromatography (GPC) and measure.SEC requires to make polymer pass through the GPC chromatography column.Hole dimension in the post is suitable for specific polymer molal weight scope.When polymer when the pillar wash-out, less polymer chain enters in the described hole, and therefore long polymer chain at first wash-out come out.The polymer of wash-out can detect by a series of detectors, comprises differential refraction index, ultraviolet ray, infrared rays and exaporative light scattering.Described analysis provides the molar mass distribution of polymer samples.By relatively, obtain the molar mass average number (Mw, Mn, Mz) of specific statistics with elution time and professional standard polymer with narrow molar mass distribution and known molal weight.
When incrustation scale inhibition unit was the polyacrylic acid unit, weight average molecular weight was preferably 2000 to 7000g/mol.
Can also mention copolymer of the present invention can provide with the form (providing the salt of (partly) neutralization) of acid or neutralization.The pH that provides is determined by series of factors, comprises the formation mineralogy of squeeze note chemicals.
The amount of polymer internal labeling unit
Polymer of the present invention comprises the indexing unit of effective detection limit.For example, for described indexing unit, described copolymer can have mole for the highest 5% but advantageously be 0.01 to 0.2% indexing unit.
Described scale inhibitor is introduced in the composition usually, and for example a kind of fluid both can be to flow into logistics, also can be squeeze note composition, for example squeeze note fluid.
Described fluid is water-based fluid preferably, and the seawater base fluid is not still got rid of other fluids usually.For example can make spent glycol or glycol ether based solvent.Some the useful fluid recipes that is used for squeeze treatment is provided in document WO 98/30783, and it is incorporated herein by reference.
The scale inhibitor of the present invention use that can be bonded to each other, and/or unite use with other water treatment agents, described other water treatment agents comprise: surfactant, anion surfactant (C10-20 alkylbenzenesulfonate for example for example, the C10-20 alkene sulfonate, the C10-20 alkyl sulfate, 1 to 25 mole of ether sulfate of C10-20 alkyl, the C10-20 alkane sulfonate, the C10-20 soap, the C10-20 alkylphenol sulfate, sulfosuccinate, sulphosuccinamate, lignosulphonates, fatty ester sulfonate, C10-20 alkyl phenyl ether sulfate, C10-20 alkyl alcohol acid amides sulfate, C10-20 α sulfofatty acid salt, the C10-20 acyl sarcosinates, isethionate, the C10-20 acyl taurine salt, C10-20 alkyl phosphoric acid hydrogen salt), non-ionic surface active agent (for example ethoxylation and/or propoxylation C10-20 alcohol, ethoxylation and/or propoxylation C10-20 carboxylic acid, alkanolamide, amine oxide and/or C10-20 acyl group sorbitan and/or glycerol ethoxylate), amphoteric surfactant (betaine for example, sulfobetaines and/or quaternised imidazoline), and/or cationic surfactant (zephiran salt for example, C10-20 alkyl trimethyl ammonium salt and/or C10-20 alkyl trimethyl or three (methylol) microcosmic salt); Sequestering agent, chelating agent, corrosion inhibitor and/or other thresholds (threshold) reagent (for example sodium phosphate trimer, sodium ethylene diamine tetracetate, sodium nitrilo triacetate, tetrapotassium pyrophosphate, acetyl di 2 ethylhexyl phosphonic acid and its salt, trimethylene ammonium phosphate and its salt, ethylenediamine tetramethylene phosphonic acid and its salt, diethylenetriamines five (methylene phosphonic acid) and its salt); The mixture of tolyl-triazole and nitrate, benzoate, HHP and/or PTCB, biocide (for example four (methylol) microcosmic salt, formaldehyde, glutaraldehyde); Oxidation biocide and/or bleaching agent (for example chlorine, chlorine dioxide, hydrogen peroxide, sodium perborate); Foam control reagent is silicone antifoam agent for example; Oxygen scavenger is hydrazine and/or azanol for example; PH control and/or buffer be amine, borate, citrate and/or acetate for example; Chromic salts; Zinc salt; And/or other water treatment agents for example polymeric dispersant and flocculant, comprise poly, polyacrylic acid and polyvinylsulfonic acid and its salt, starch and/or carboxymethyl cellulose, and/or molybdate.Prescription provided by the invention comprises the invention described above product and any above-mentioned known water treatment agent of effective dose.This class prescription can for example comprise the product of the present invention of 5 to 95% weight and one or more above-mentioned any water treatment agents of 5 to 90% weight.
More specifically, described fluid can further comprise and is selected from following additive:
-corrosion inhibitor (imidazoline and quaternary ammonium salt)
-hydrate inhibitor (for example methyl alcohol) and cinetic inhibitor be anti-agglomerating agent for example,
-asphalitine inhibitor
-wax inhibitor
-biocide (THPS for example, for example Rhodia with
PS sells)
-demulsifying agent
-surfactant,
-other scale inhibitors.
The aqueous solution of scale inhibitor can be used for implantation step (squeeze treatment); Usually the concentration of scale inhibitor is 0.5 to 20%, preferred 2 to 10% of aqueous solution weight.When the production water from oil well begins to demonstrate the scale inhibitor level of reduction, then require further squeeze treatment.Usually, under the inhibitor level that is higher than about 25ppm (producing in the water or in formation water) with the incrustation scale inhibitory action of remaining valid.The control of amount that incrustation scale is suppressed polymer is effective more, and the level of producing the scale inhibitor in the water before requiring additional treatments can be low more.Reprocessing comprises: the time interval with selection is injected into underground containing in the oil stratum with the additional water-soluble polymer aqueous solution, so that the amount that can effectively keep the inhibiting water-soluble polymer of incrustation scale to be provided.
Use for squeeze treatment, described fluid can be united use with preposition chemicals, particularly surfactant and/or emulsifier.These chemicals applied before the squeeze note inhibitor usually, to help to be adsorbed onto on the rock and to minimize emulsification problem.Useful preparation and process have instruction in document WO 98/30783.
Further mention: the water oil of extraction reclaims complete crude oil or the inorganic residues that separates with produced fluid that do not have that fluid can comprise trace.
Consumption (scale inhibitor)
The amount of the polymer that uses depends on application usually.Use for squeeze treatment, copolymer is applied to the down-hole as the concentrated solution in the appropriate carriers fluid usually.The typical concentration of inhibitor will be 1-50%, more preferably 5-20%.Carrier fluid can be that seawater, recovered water, aquifer water, film are handled water, desulfurization water for example, perhaps above-mentioned mixture.Selectively, described carrier fluid can be based on the carrier fluid of compatible solvent, for example ethylene glycol or glycol ether.
Minimum inhibitor concentration (MIC) changes with the water chemistry situation usually, but usually within the 1-500ppm scope, the fouling environment is abominable more, and the concentration of requirement is high more.
Claims (15)
1. method that makes oilfield stimulation, comprise that the inflow stream with a kind of fluid injects the Petroleum Production well that is connected with the oil field, replace described oil, and reclaim the outflow logistics of the fluid that comprises described oil, wherein, at least two logistics are injected at least two production areas of an oil well, perhaps inject at least two different Petroleum Production wells, to flow out logistics from described two districts or well at least two before reclaiming merges, but the scale inhibitor that wherein will have the test section is introduced described oil field and/or described fluid, it is characterized in that, use two kinds of different scale inhibitors, be used for described two districts or well, but described different scale inhibitor has different test sections, but these different test sections can be distinguished by analyzing.
2. the process of claim 1 wherein that described different scale inhibitor is introduced in the fluid.
3. the method for claim 1, wherein before volume increase,, enter different oil fields by forcing described different scale inhibitor according to squeeze treatment, described different scale inhibitor is introduced described oil field, and described scale inhibitor is released in described outflow logistics.
4. any one method of claim 1-3, but wherein said different test section is selected from:
A) atom mark part comprises that at least one is selected from the atom of boron, silicon and germanium,
B) derived from acetoxyl group-styrene or derived from the part of o-allyl phenol,
C) derived from the part of monomer with following general formula:
X
2C＝CYY’，
Wherein:
-X is same or different, is hydrogen atom or C
1-C
4Alkyl group,
-Y is hydrogen atom or C
1-C
4Alkyl group,
-Y ' is the group with general formula-L-Arom, wherein
-L is covalency keyed jointing or the organic linking group of divalence, and the organic linking group of this divalence randomly comprises hetero atom, and
-Arom is the group that comprises at least two conjugation aromatic rings, and described ring comprises the carbon atom of conjugation and randomly nitrogen or oxygen atom, and the hydrogen atom or the substituting group that are connected to described carbon atom,
D) pass through the unit of derived from ethylene base benzyl chloride and the part that following substance reaction obtains after the polymerization:
The amino pyrene-1,3 of-8-, the 6-trisulfonic acid, perhaps
-9-(2-(carbethoxyl group) phenyl)-3, two (ethylamino-)-2 of 6-, 7-dimethyl xanthene chloride (rhodamine 6G), perhaps
The blue CMAC of-CellTracker,
The perhaps salt of this part,
E) derived from by the amino pyrene-1,3 of vinyl chloride and 8-, the part of the monomer of 6-trisulfonic acid or the preparation of its reactant salt,
F) comprise the part of at least one phosphate or phosphonate groups,
G) comprise the part of at least one sulfonate or sulfonic acid group.
5. the method for claim 4, wherein said acetoxyl group-styrene is 4-acetoxyl group-styrene.
6. the method for claim 4, wherein Arom is the group that comprises at least three conjugation aromatic rings.
7. any one method of claim 1-3, but the described different scale inhibitor that wherein has different test sections is to comprise the incrustation scale that incrustation scale suppresses unit and the different indexing unit with different piece to suppress polymer, and wherein said indexing unit is selected from:
A) atom indexing unit comprises that at least one is selected from the atom of boron, silicon and germanium,
B) derived from acetoxyl group-styrene or derived from the unit of o-allyl phenol,
C) derived from the unit of monomer with following general formula:
X
2C＝CYY’，
Wherein:
-X is same or different, is hydrogen atom or C
1-C
4Alkyl group,
-Y is hydrogen atom or C
1-C
4Alkyl group,
-Y ' is the group with general formula-L-Arom, wherein
-L is covalency keyed jointing or the organic linking group of divalence, and the organic linking group of this divalence randomly comprises hetero atom, and
-Arom is the group that comprises at least two conjugation aromatic rings, and described ring comprises the carbon atom of conjugation and randomly nitrogen or oxygen atom, and the hydrogen atom or the substituting group that are connected to described carbon atom,
D) pass through the unit of derived from ethylene base benzyl chloride and the unit that following substance reaction obtains after the polymerization:
The amino pyrene-1,3 of-8-, the 6-trisulfonic acid,
-9-(2-(carbethoxyl group) phenyl)-3, two (ethylamino-)-2 of 6-, 7-dimethyl xanthene chloride (rhodamine 6G), perhaps
The blue CMAC of-CellTracker,
Perhaps the salt of this part and
E) derived from by the amino pyrene-1,3 of vinyl chloride and 8-, the unit of the monomer of 6-trisulfonic acid or the preparation of its reactant salt.
8. the method for claim 7, wherein said acetoxyl group-styrene is 4-acetoxyl group-styrene.
9. the method for claim 7, wherein Arom is the group that comprises at least three conjugation aromatic rings.
10. the method for claim 7, wherein said different scale inhibitor at least a are that the incrustation scale of mark suppresses polymer, and it comprises the indexing unit derived from the 9-vinyl anthracene.
11. the method for claim 7, wherein said incrustation scale suppress the unit derived from being selected from following monomer:
-vinyl sulfonic acid, perhaps vinylsulfonate,
-vinyl phosphonate, perhaps vinyl phosphonic hydrochlorate,
-acrylic acid, methacrylic acid,
-maleic anhydride, maleic acid,
-styrene-p-sulfonic acid, perhaps styrene sulfonate,
-acrylamido-2-methyl propane sulfonic acid (AMPS) and
The mixture of-above-mentioned monomer.
12. any one method of claim 1-3, it comprises the amount of the different scale inhibitors in the fluid that mensuration reclaims or from the amount of a kind of fluid of wherein obtaining, if and the amount of scale inhibitor is lower than set-point, then solves the incrustation scale that in district that uses described scale inhibitor or well, occurs and form problem.
13. any one method of claim 1-3, wherein said scale inhibitor is introduced in the water-based fluid, or more kinds of scale inhibitor is introduced in the described fluid, and perhaps described scale inhibitor is introduced in the oil field according to squeeze treatment.
14. any one method of claim 1-3, wherein said scale inhibitor can be distinguished by single analytical method.
15. the method for claim 14, wherein said single analytical method is a fluorometry.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48227103P | 2003-06-25 | 2003-06-25 | |
| US60/482,271 | 2003-06-25 | ||
| US60/482,257 | 2003-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1846040A CN1846040A (en) | 2006-10-11 |
| CN100538002C true CN100538002C (en) | 2009-09-09 |
Family
ID=37031104
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800245431A Active CN100486914C (en) | 2003-06-25 | 2004-06-25 | Tagged scale inhibiting polymers, compositions comprising the same, and method for preventing or controlling scale formation |
| CNB2004800245484A Expired - Fee Related CN100538002C (en) | 2003-06-25 | 2004-06-25 | Use different scale inhibitors to make the method for oilfield stimulation |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800245431A Active CN100486914C (en) | 2003-06-25 | 2004-06-25 | Tagged scale inhibiting polymers, compositions comprising the same, and method for preventing or controlling scale formation |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN100486914C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103476900B (en) * | 2011-01-19 | 2016-08-17 | 罗迪亚运营公司 | There is fouling inhibitor and their application in oil field of different absorption curve |
| CN110054266B (en) * | 2019-05-14 | 2021-08-31 | 广东天赐水处理科技有限公司 | Deep-cleaning sewage treatment agent |
| CN112065379A (en) * | 2020-10-12 | 2020-12-11 | 西南石油大学 | Method for predicting scaling damage of water injection well |
-
2004
- 2004-06-25 CN CNB2004800245431A patent/CN100486914C/en active Active
- 2004-06-25 CN CNB2004800245484A patent/CN100538002C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1846040A (en) | 2006-10-11 |
| CN1842496A (en) | 2006-10-04 |
| CN100486914C (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2307233C2 (en) | Method for oil field excitation with the use of different scaling inhibitors | |
| US8871691B2 (en) | Methods of treating flowback water | |
| RU2555970C2 (en) | Compositions for wells treatment with sustained release for use in well treatment liquids | |
| US6995120B2 (en) | Scale control composition for high scaling environments | |
| US8586511B2 (en) | Scale inhibiting well treatment | |
| CN103476900A (en) | Families of scale-inhibitors having different absorption profiles and their application in oilfield | |
| EP2429957B1 (en) | Tagged scale inhibitors | |
| CN100538002C (en) | Use different scale inhibitors to make the method for oilfield stimulation | |
| BRPI0620391B1 (en) | INCRUSTATION INHIBITOR, METHOD FOR TREATING INCRUSTATION AND METHOD OF INCREASING BIODEGRADABILITY OF AN ANIMIC POLYMER | |
| EP3124510A1 (en) | Method for obtaining random terpolymers derived from itaconic acid and aconitic acid, and/or the isomers thereof, and/or sodium alkenyl sulphonates, and use of the resulting product | |
| CA2758782A1 (en) | Fluid treatment systems, compositions and methods for metal ion stabilization in aqueous solutions and/or enhanced fluid performance | |
| US20220145169A1 (en) | Subterranean formations | |
| EP4348004A1 (en) | Tagged polymer and method | |
| CA3193015A1 (en) | Tagging agents, anti-scalant polymer compositions, and methods | |
| CN1204380A (en) | Scale inhibition by squeeze application of phosphonomethylated polyamine inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090909 Termination date: 20200625 |