CN1842496A - Tagged scale inhibiting polymers, compositions comprising the same, and method for preventing or controlling scale formation - Google Patents
Tagged scale inhibiting polymers, compositions comprising the same, and method for preventing or controlling scale formation Download PDFInfo
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- CN1842496A CN1842496A CN 200480024543 CN200480024543A CN1842496A CN 1842496 A CN1842496 A CN 1842496A CN 200480024543 CN200480024543 CN 200480024543 CN 200480024543 A CN200480024543 A CN 200480024543A CN 1842496 A CN1842496 A CN 1842496A
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- Prior art keywords
- fluid
- incrustation scale
- multipolymer
- polymkeric substance
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- 229920000642 polymer Polymers 0.000 title abstract description 41
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
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- 230000003068 static effect Effects 0.000 description 4
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- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical class [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000007421 fluorometric assay Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- QBPHJWZNDSKPJL-UHFFFAOYSA-N m-diisopropylbenzene hydroxyhydroperoxide Chemical compound OOO.CC(C)C1=CC=CC(C(C)C)=C1 QBPHJWZNDSKPJL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Abstract
The invention relates to tagged scale-inhibiting polymers, to compositions comprising said polymers, and to a method for preventing or controlling scale formation in systems comprising said fluids. The tagging units are units deriving from a monomer having formula X2C=CYY', wherein X, which is identical or different, is a hydrogen atom, or a Cl-C4 alkyl group, Y is a hydrogen atom or a C1-C4 alkyl group, Y' is a group having formula -L-Arom, wherein L is a covalent bound or a divalent organic linking group optionally comprising. heteroatoms, and Arom is a group comprising at least two conjugated aromatic rings, preferably at least three, said rings comprising conjugated carbon atoms, and, linked to said carbon atoms, hydrogen atoms or substituants.
Description
Background technology
The incrustation scale that the present invention relates to tape label suppresses polymkeric substance, comprises the composition of described polymkeric substance and prevent or be controlled to comprise the method that forms incrustation scale in the described fluidic system.
Wrap in the aqueous system at great majority, forming incrustation scale is the problem that needs solution.When the physical environment of water changes and will form incrustation scale when causing some compound to surpass solubility limit.For example, the composition of pH, temperature, pressure or water changes and all may cause the deposition of incrustation scale.In field produces, the most debatable incrustation scale is metal sulfate and carbonate, particularly barium sulfate.Form incrustation scale and can cause many problems, for example it can reduce the heat transfer of boiler and condenser, and may blocking pipe.In oil recovery, more importantly in secondary oil recovery (wherein for replace crude oil and with the stratum repressurize, water is injected in the oil well), the formation of incrustation scale may cause that the hole in pipeline and the tryphine stops up, and therefore reduces or even stops flowing of oil.
In order to solve the problem that forms incrustation scale, for example polymkeric substance, phosphonate, poly-phosphate are known to use incrustation scale to suppress chemical.For different systems, processing horizontal is different, is generally less than 1ppm until hundreds of ppm.Incrustation scale suppresses chemical and is used in the various industrial application that make water, for example petroleum industry is used, and comprises secondary oil production, cooling tower, boiler, hot desalting plant, membrane separation process, mineral ore extraction, paper pulp manufacturing, papermaking and underground heat power generation equipment or the like.
In most of these were used, incrustation scale suppressed chemical and can use simple chemical charging system directly to add described system.For secondary oil recovery, incrustation scale suppresses chemical and can be applied in the oil-bearing formation by " squeeze treatment ".Squeeze treatment comprises scale inhibitor is pumped into the oil production 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 described scale inhibitor is released in the fluid of the described oil of displacement.Scale inhibitor can be applied in water base or the non-aqueous media, as the form of solution, emulsion or packaged products.Incrustation scale suppresses chemical can also be used to oil field, upper strata (topside) technology.
Purpose is to prevent from or be controlled to use in the described fluidic system to form incrustation scale.
Has only the formation that suppresses to control when chemical exists with the processing horizontal in the useful range of the regulation that is in product incrustation scale when incrustation scale.Yet the water system that great majority need incrustation scale control to handle has the liquid loss, and treated water is lost from described system.In addition, scale inhibitor may lose by for example absorption or degraded.Therefore, in order to remedy this loss, need the make up water scale inhibitors.In addition, for squeeze treatment, the scale inhibitor concentration in the produced fluid will reduce along with the past of time, carry out multiple " squeeze note again " operation up to needs.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 chemical, especially polymkeric substance is difficult in the ppm level always.Recently, the problem of analyzing becomes more outstanding at the seabed tieback that is used for oil production, because subsea-completed well uses several one wells on the seabed usually, merged from the effusive fluid of these wells at this, and the fluid that merges by pipeline be transported to nearest may be at the production vessels beyond tens miles.In this case, needs are used the one well of incrustation scale control chemical treatments that to be analyzed individually.
Therefore, need the method for good analysis scale inhibitor chemical, this is at least because one of following reason:
-for the concentration that guarantees the scale inhibitor chemical does not exceed useful range,
-in order to optimize dosage, and/or
-for fear of because unwanted squeeze note again and stop to produce in fact also.
Because concentration low (the highest hundreds of ppm), the concentration of therefore measuring scale inhibitor chemical, especially polymkeric substance is difficult, has advised using polymkeric substance tape label or " tagging " for this reason, and it has the group that is easy to detect.Numerous reference teaches the incrustation scale of mark suppress the preparation of polymkeric substance and the measuring method of its amount.
Reference EP 157465 has described the multipolymer that comprises the group that reacts with diazonium salt, can pass through its amount of colorimetric method for determining like this.
Reference WO 01/44403 has described the multipolymer that comprises pyrene-deriveding group, so that measure its amount by fluorometry.
The present invention relates to the other tagged polymers more superior than prior art.Described polymkeric substance is specially adapted to oil recovery system, but also can be used for any wherein incrustation scale control additive detection is the useful system that makes water, for example boiler, the extraction of cooling tower mineral ore, paper pulp manufacturing, papermaking, underground heat power generation equipment, membrane separation process and hot desalting plant.The polymkeric substance of described mark and described mark has good salt tolerant (water) property and temperature tolerance.They even the compound in being included in described fluid also are detectable in the presence of oxidation inhibitor or the non-refiltered oil for example.
Summary of the invention
The present invention relates to comprise the incrustation scale inhibition polymkeric substance that incrustation scale suppresses the mark of unit and indexing unit, wherein said indexing unit is derived from the monomeric unit 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 heteroatoms, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic nucleus, and described ring comprises conjugated carbon atom and randomly nitrogen or Sauerstoffatom, and the hydrogen atom or the substituting group that are connected to described carbon atom.
On the other hand, the incrustation scale that the present invention relates to comprise described mark suppresses the composition of multipolymer, fluid for example, for example process water fluid or oil-recovery fluid or squeeze treatment composition, squeeze note fluid for example, and the incrustation scale that relates to described mark suppresses the purposes of polymkeric substance in described composition, for example purposes in fluid or squeeze treatment product.The process water fluid is meant the fluid in for example cooling water system, the especially cooling tower, boiler feed water, the fluid in the hot desalting plant, fluid in the membrane separation process, fluid in the underground heat power generation, the fluid during mineral ore is extracted, the fluid in paper pulp manufacturing and the papermaking.
On the other hand, the present invention relates to prevent or control the method that incrustation scale forms.Described method, it is particularly suitable for wherein existing water or water-based fluid round-robin system, may further comprise the steps:
-will suppress polymkeric substance at the incrustation scale of the mark of the incrustation scale amount of suppression in the described fluid and add the oil field, perhaps force the incrustation scale of mark to suppress polymkeric substance and enter the oil field, wherein will be recycled at fluid described in the described oil field by for example squeeze treatment,
-measure periodically, constantly or continuously the mark in the described fluid amount and
-when observed value was lower than set-point, the incrustation scale that further adds some mark periodically, constantly or continuously suppressed multipolymer, and/or force the incrustation scale inhibition polymkeric substance of described mark to enter described oil field again.
The invention still further relates to described incrustation scale and suppress the purposes that polymkeric substance is used to prevent or control incrustation scale formation.
Application Areas of the present invention comprises various equipment or the purposes that make water; For example water vapor or hot water boiler, paper pulp manufacturing and papermaking, cooling system is cooling tower for example, desalting plant (heat or reverse osmosis), underground heat equipment, membrane sepn, mineral ore is extracted.Application Areas also comprises oil recovery, preferred secondary oil recovery, and oil production equipment.The type of the incrustation scale that runs in these are used comprises: carbonate, for example lime carbonate, magnesium or strontium, vitriol, for example barium sulfate and Strontium Sulphate, calcium sulfate, oxalate, caoxalate for example, phosphoric acid salt, calcium phosphate for example, fluorochemical, sulfide, silicon-dioxide and silicate, naphthenate (naphtlenate), for example calcium naphthenate.
Incrustation scale of the present invention suppresses polymkeric substance can also have dispersing agent performance, and it can be used for controlling because of silting up that particulate matter causes.In addition, they can be applied in the clay slip, are used for ceramic industry, to improve rheology and processing property.Described polymkeric substance also can be used for the control corrosion, for example ferrous metal corrosion.
Described incrustation scale suppresses polymkeric substance can be used alone, perhaps be used in combination, for example incrustation scale and corrosion inhibitor, dispersion agent, oxygen scavenqer, biocide, flocculation agent, hydrate inhibitor, bituminous matter inhibitor, biocide, tensio-active agent, demulsifying compound with other Water Treatment Chemicals or other production additives.The fluid that comprises the incrustation scale inhibition polymkeric substance of mark of the present invention can also comprise other impurity, for example residual organic, iron, divalent cation, muriate.The incrustation scale of described mark suppresses polymkeric substance can be detected in the presence of these impurity.
Embodiment
Definition
Polymkeric substance is meant the macromolecular chain that comprises repeating unit.Multipolymer is meant and comprises repeating unit and have at least two kinds of different unitary polymkeric substance.Multipolymer comprises the polymkeric substance with two kinds of different repeating units, the polymkeric substance (being sometimes referred to as ter-polymers) with three kinds of different repeating units or the polymkeric substance with more kinds of repeating units.
" MIC " refers to minimum inhibitor concentration.MIC can be according to NACS standard TM 0197-97, 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 Sulphate are precipitated out from solution ability (for the oil and natural gas production system).
The incrustation scale of mark suppresses multipolymer
The incrustation scale of mark of the present invention suppresses polymkeric substance and comprises at least two kinds of different unit: incrustation scale suppresses unit and indexing unit.Because described polymkeric substance comprises these two kinds of different unit at least, therefore described polymkeric substance is also referred to as multipolymer.Incrustation scale suppresses the formation that the unit prevents incrustation scale.Indexing unit can detect by analytical procedure.Do not get rid of the situation that indexing unit prevents that equally incrustation scale from forming.Do not get rid of incrustation scale and suppress the situation that the unit also can be detected.
Polymkeric substance of the present invention prepares by monomer polymerization.
Any polymerization process all can be used for making described polymkeric substance.Free radical polymerisation process is preferred.The method that is fit to comprises water base body/dispersion polymerization, solution polymerization or letex polymerization.Preferred polymerization process is solution polymerization.According to the method, the water adding is equipped with the reaction vessel of mechanical stirrer and water condenser, and is heated to 90 ℃.Can perhaps can add afterwards to wherein adding polymerization starter.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-transfer 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.
Indexing unit
The indexing unit of polymkeric substance of the present invention is selected from:
-derived from monomeric unit 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 heteroatoms, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic nucleus, and described ring comprises conjugated carbon atom and randomly nitrogen or Sauerstoffatom, 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 nucleus.The conjugation aromatic nucleus 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)
Other unit comprise derived from following unit: α-vinyl naphthalene, 1-vinylpyrene, 4-vinyl-9,10-diphenylanthrancene, 3-vinyl phenanthrene, 9-vinyl acridine.
Described indexing unit can detect by any appropriate means, and for example fluorometry for example uses the fixed wave length photofluorometer.Usually, detection is carried out under polymkeric substance 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 working curve contrast that obtains from polymer samples, can determine polymer concentration with concentration known.
Following table has shown the example of the wavelength of some polymkeric substance.
| Multipolymer | Excitation wavelength (nm) | Emission wavelength (nm) |
| AA*-0.1 mole %9-vinyl anthracene multipolymer | 260 | 410 |
| AA*-0.05 mole %9-vinyl anthracene multipolymer | 260 | 410 |
| AA*-0.01 mole %9-vinyl anthracene multipolymer | 300 | 380 |
* vinylformic 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,
-vinylformic acid,
-methacrylic acid,
-vinyl acetate,
-vinyl alcohol,
-unsaturated list or omega-dicarboxylic acids or acid anhydrides, for example maleic anhydride, toxilic acid, fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid, Ba Dousuan, iso-crotonic acid, angelicic acid, tiglic acid,
-vinylchlorid,
-vinylbenzene-p-sulfonic acid, perhaps styrene sulfonate,
-acrylamido-2-methyl propane sulfonic acid (AMPS),
-HPAA (HPA),
-Hypophosporous Acid, 50 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 monomerss (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 multipolymer 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 starter, 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 basic metal, alkaline-earth metal or other polyvalent metals, ammonium or organic bases, 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 phosphonic acids (VPA) or vinylidene-1, the unit of the affixture of 1-di 2 ethylhexyl phosphonic acid (VDPA) and Hypophosporous Acid, 50 or its salt.This class group or unit are described in the document EP 861846.Group that other are possible or unit are described among the GB 1458235.These other groups or unit can help to detect described polymkeric substance, and/or help the incrustation scale restraining effect.
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 polymkeric substance.
Molecular weight data and other parameters
Polymkeric substance 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 polymkeric substance or multipolymer can be passed through size exclusion chromatography,/gel permeation chromatography (GPC) and measure.Size exclusion chromatography, requires to make polymkeric substance downwards by the GPC packing.Hole dimension in the post is suitable for specific polymkeric substance molar mass scope.When polymkeric substance 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 polymkeric substance of wash-out can detect by a series of detectors, comprises differential refractive index, ultraviolet ray, infrared rays and exaporative scattering of light.Described analysis provides the molar mass distribution of polymer samples.By elution time and the specialized standard polymkeric substance with narrow molar mass distribution and known molar mass are compared, obtain the molar mass average number (Mw, Mn, Mz) of specific statistics.
When incrustation scale inhibition unit was the polyacrylic acid unit, weight-average molecular weight was preferably 2000 to 7000g/mol.
Can also mention multipolymer of the present invention can provide with acid or neutral form (providing (partly) neutral salt).The pH that provides is determined by series of factors, comprises the formation mineralogy of squeeze note chemical.
The unitary amount of polymkeric substance internal labeling
Polymkeric substance of the present invention comprises the indexing unit of effective detection limit.For example, for described indexing unit, described multipolymer can have molar weight for the highest 5% but advantageously be 0.01 to 0.2% indexing unit.
Composition-fluid
Described incrustation scale suppresses polymkeric substance and is introduced into usually in the composition, for example in the fluid.According to an embodiment, described fluid is contained in or is intended in industrial water system or the process system.The example of industrial water system comprises boiler, and cooling system is the cooling system in industry or the chemical process for example, for example cooling tower, desalting plant (based on heat or film), underground heat power generation, irrigation system, the mineral ore extraction system, paper pulp manufacturing or paper manufacturing systems, film separating system.
In another embodiment, described fluid is used to petroleum industry, and wherein it can be used for handling waterflood system, the seabed flow duct, and the upper strata production unit, and most preferably use " in the down-hole ", to be controlled at production wellbores neutralization fouling on every side.The method of possible down-hole configuration scale inhibitor comprises: inject continuously, by gas lift configuration, squeeze treatment, coil pipe.
It can be used for the squeeze treatment technology, and can apply by the minor diameter tubing string.It also can be placed in the shaft bottom small diameter borehole of bottom.If used squeeze treatment, the fluid that then comprises incrustation scale inhibition polymkeric substance is construed as forcing incrustation scale to suppress the fluid that polymkeric substance enters well or formation rock, and perhaps described incrustation scale suppresses the fluid that polymkeric substance 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 chemical under the recovery well and end oil production when entering the stratum, closes described well and interacts to allow chemical and formation rock, restarts production then.Described chemical 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 comparatively large vol, 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 exploitation of extensive investment.Yet the cost of squeeze treatment is huge in these wells, and major cause is to incur loss through delay to recover the oil and access charge.By contrast, inhibitor chemical 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 polymkeric substance is the stratum absorption that can improve inhibitor.
The main phase of squeeze note operation comprised with the next stage:
(i) pre-flushing: this is made up of the diluting soln of inhibitor in seawater, and it comprises tensio-active agent or demulsifying compound 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 local water and the formation of buffer zone, to avoid uncompatibility any and the high density inhibitor that injects, particularly all the more so when relating to high salinity/high-calcium ionic local water.Described pre-flushing can also be removed residual face of land oil, to improve wettability.
(ii) inhibitor injects: main inhibitor treatment agent is normally at the 5-10% of seawater activity inhibitor.With maximum inhibitor Adsorption Modelization (according to thermoisopleth, annotate (corefloods) or obtain by historical matching method more accurately by core) and the surface area modeling 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 chemical.
(iii) flushing (over-flush) 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 surface area and improved adsorption levels.This also replaces inhibitor the stratum of the heat that can carry out bigger absorption near the refrigerative wellhole.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 wettability.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 shut-in time, depend on that inhibitor absorption reaches the needed time span of balance.Under higher temperature, adsorption rate is higher, so the turn-off time can reduce.Modeling 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.
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.The fluidic prescription that is used for squeeze treatment that some is useful is provided in document WO 98/30783.
The polymkeric substance of the present invention use that can be bonded to each other, and/or unite use with other water conditioners, described other water conditioners comprise: tensio-active agent, anion surfactant (C10-20 alkylbenzene sulfonate for example for example, the C10-20 alkene sulfonate, the C10-20 alkyl-sulphate, 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, Sulfite lignin, fatty ester sulfonate, C10-20 alkyl phenyl ether sulfate, C10-20 alkyl alcohol acid amides vitriol, C10-20 α sulfofatty acid salt, the C10-20 acyl sarcosinate, isethionate, the C10-20 acyl taurine salt, C10-20 alkylphosphonic acid carboxylic acid hydrogen salt), nonionogenic tenside (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), amphoterics (trimethyl-glycine for example, sultaine and/or quaternised tetrahydroglyoxaline), and/or cats product (zephiran salt for example, C10-20 alkyl trimethyl ammonium salt and/or C10-20 alkyl trimethyl or three (methylol) phosphorus salt); Sequestering agent, sequestrant, corrosion inhibitor and/or other thresholds (threshold) reagent (polymkeric substance for example, for example aminometholine phosphonate polymer, polyacrylic acid, or non-polymer reagent, for example tripoly phosphate sodium STPP, sodium ethylene diamine tetracetate, sodium nitrilo triacetate, tetrapotassium pyrophosphate, acetyl di 2 ethylhexyl phosphonic acid and its salt, trimethylene phosphonic ammonium and its salt, ethylenediamine tetraacetic (methylene phosphonic acid) and its salt, diethylenetriamine five (methylene phosphonic acid) and its salt); The mixture of tolyl-triazole and nitrate, benzoate, HHP and/or PTCB, biocide (for example four (methylol) phosphorus salt, formaldehyde, glutaraldehyde, DENPA, bromopol isothiazoronal); Oxidation biocide and/or SYNTHETIC OPTICAL WHITNER (for example chlorine, dioxide peroxide, hydrogen peroxide, Sodium peroxoborate); Foam control reagent is silicone antifoam agent for example; Oxygen scavenqer is hydrazine and/or azanol for example; PH control and/or buffer reagent be amine, borate, Citrate trianion and/or acetate for example; Chromic salts; Zinc salt; And/or other water conditioners for example polymeric dispersant and flocculation agent, comprise polymaleic acid, 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 conditioner of significant quantity.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 conditioners of 5 to 90% weight.
More specifically, described fluid can further comprise and is selected from following additive:
-corrosion inhibitor (tetrahydroglyoxaline and quaternary ammonium salt)
-hydrate inhibitor (for example methyl alcohol) and cinetic inhibitor be anti-agglomerating agent for example,
-bituminous matter inhibitor
-wax inhibitor
-biocide (for example THPS is for example sold with Tolcide PS by Rhodia)
-demulsifying compound
-tensio-active agent,
-other scale inhibitors.
Water filling is a normally used technology in the oil-recovery operations.Water is injected into the local water repository by injecting well under pressure; This process drives oil and enters recovery well by mineral deposit and rock stratum.That in off-shore operation, be easy to obtain and comprise a large amount of dissolved saltses, for example vitriol as the seawater of the injection water in the water flood operations usually.The interaction of injecting the local water in water (not having under the situation of effective scale inhibitor) and described repository will produce undesirable inorganic deposition (mainly being the dirty salt of causing of calcium sulfate, barium sulfate and Strontium Sulphate), and it finally stops up pipe, valve and the pump of oil recovery process equipment.The sedimentary supplementary condition that aggravation causes dirty salt are included in barium, strontium, calcium or the iron ion of the pressure, high temperature and the high density 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, comprise the injecting step of scale inhibitor then; Succeeded by adding additional seawater (finishing last rinse step), so that scale inhibitor further is distributed in the described repository, 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 oil production equipment up big more.
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 of the minimum inhibitor concentration that is higher than favourable about 25ppm (producing in the water or in local water) (MIC is measured by static bottle examination method), with the incrustation scale restraining effect of remaining valid.The control of amount that incrustation scale is suppressed polymkeric substance is effective more, and the level of producing the scale inhibitor in the water before requiring additional processing can be low more.Re-treatment comprises: the timed interval with selection is injected into subterranean containing in the oil stratum with the additional water-soluble polymers aqueous solution, so that the amount that can effectively keep the inhibiting water-soluble polymers of incrustation scale to be provided.
Use for squeeze treatment, described fluid can be united use with spearhead chemical, particularly tensio-active agent and/or emulsifying agent.These chemical applied before the squeeze note inhibitor usually, to help to be adsorbed onto on the rock and to minimize emulsification problem.Useful prescription and process have instruction in document WO 98/30783.
Further mention: the water recovery of oil fluid of extraction can comprise incomplete and the isolating crude oil of produced fluid or the inorganic residues of trace.
The present invention allows to carry out the marine analysis of successive.
Consumption (polymkeric substance)
The amount of the polymkeric substance that uses depends on application usually.Use for squeeze treatment, multipolymer is applied to the down-hole as the strong solution in the appropriate carriers fluid usually.The typical concentration of inhibitor will be 1-50%, more preferably 5-20%.Carrier fluid can be seawater, recovered water, aquifer water, film treating water, desulfurization water for example, perhaps above-mentioned mixture.Selectively, described carrier fluid can be based on for example carrier fluid of ethylene glycol or glycol ether of compatible solvent, particularly in severe cold environment, as in Russia and Canadian, all the more so.
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.
For non-oil field industrial application, described product is introduced directly into current usually, is given in concentration in the water between 0.1 to 1000ppm.
Prevent or control the method that incrustation scale forms
The invention still further relates to prevent or be controlled at and have fluid circulation, preferably form the method for incrustation scale in the water-based fluid round-robin system, it may further comprise the steps:
-will suppress polymkeric substance at the incrustation scale of the mark of the incrustation scale amount of suppression in the described fluid and add the oil field, perhaps to force the incrustation scale of mark to suppress polymkeric substance and enter the oil field, wherein said fluid will be recycled,
-measure periodically, constantly or continuously the mark in the described fluid amount and
-when observed value was lower than set-point, the incrustation scale that further adds some mark periodically, constantly or continuously suppressed multipolymer, and/or force the incrustation scale inhibition polymkeric substance of described mark to enter described oil field again,
Wherein said incrustation scale suppresses the incrustation scale inhibition multipolymer that multipolymer is a mark.
The example of system comprises:
-industrial water system for example comprises or has the system of boiler or process water.
-cooling tower system,
The system that comprises in-the desalting plant,
The system that-underground heat power generation comprises,
-mineral ore is extracted the system that comprises,
The system that comprises in manufacturing of-paper pulp or the papermaking.
Other examples of system comprise: in the oil production well and near the system that comprises the recovery well boring, wherein can comprise squeeze treatment use, by means of the configuration of minor diameter tubing string or in rat hole, place.Described system can be the squeeze treatment system, and perhaps wherein incrustation scale suppresses the system that polymkeric substance is introduced into the production fluid that is used for replacing oil.
Measure the amount of mark, and the scale inhibitor polymkeric substance that further adds mark, can be advantageously after with described fluid and described separated from petroleum, and before in being injected into described well, on described fluid, carry out.
The present invention specific, non-restrictive example provides as follows.
Embodiment 1: the incrustation scale of preparation mark suppresses multipolymer: the multipolymer of vinylformic acid (AA) and vinyl chloride (VBC) changes into the multipolymer of vinylformic acid (AA) and rhodamine 6G (R6G)
Synthesizing in two steps of this polymkeric substance carried out.First step is the copolymerization of AA and VBC.After the polymerization, the nucleophilic substitution reaction by VBC is connected to the rhodamine 6G fluorescence molecule on the described polymkeric substance.
In four necks that are equipped with mechanical stirrer (tetrafluoroethylene blade) and reflux exchanger, 1 liter, the round-bottomed flask that cooperates rapidly, add the 172.5g Urban water supply and as table 1A in indicate vinyl chloride (97%, Aldrich, catalog number (Cat.No.) 33,872-9).With it under agitation, in water-bath, be heated to 90 ℃ with thermopair control.In case container contents reaches temperature, use wriggling and syringe pump respectively, with the solution of the initiator (23% sodium sulfite solution) of 238.4g and chain-transfer agent (CTR), be dissolved in the 11.7g Sodium Persulfate in the 31.4g Urban water supply, with constant rate of speed, in 6 hours, be fed to jointly in the described container.After initiator/CTR charging begins 15 minutes, use peristaltic pump, with constant rate of speed, in 5.5 hours 534.8g monomer vinylformic acid is fed to (15 minutes finish before initiator/CTR charging finishes) in the container.In case polymerization is complete, temperature is brought up to 98 ℃, and container contents was refluxed 2 hours.Then container contents is cooled off.Make N
2Gas passed through described polymers soln bubbling 8 hours, to remove residual SO
2Then with 47%NaOH solution with its pH=5.1-6.1 that neutralizes, and regulate solids content to 53.0-55.0% with Urban water supply.
The final polymer physics performance of AA/VBC multipolymer is shown in table 1B.
The introducing level of table 1A:VBC in the AA multipolymer
| The polymkeric substance explanation | The gram number of the VBC that adds | VBC mole % | Suppose and introduce 100% VBC, and polymer chain Mw=4000, the amount of chlorine atom of each polymer chain |
| 02/16/A | 1.12 | 0.10 | 1, per 18 polymer chains |
| 02/16/B | 0.56 | 0.05 | 1, per 36 polymer chains |
| 02/16/C | 0.11 | 0.01 | 1, per 186 polymer chains |
The physicals of table 1B:AA/VBC multipolymer
| The polymkeric substance explanation | Test | ||
| Solids content (0.5g, 130 ℃, 1hr, 3 average)/% | Brookfield viscosity (LV3,30rpm, 25 ℃)/cPs | pH(5％) | |
| 02/16/A (acid) | 63.8 | 3120 | 2.89 |
| 02/16/A | 53.7 | 760 | 5.23 |
| 02/16/B (acid) | 65.5 | 4150 | 2.92 |
| 02/16/B | 52.3 | 630 | 5.28 |
| 02/16/C (acid) | 62.5 | 11860(LV4) | 2.89 |
| 02/16/C | 53.8 | 2800 | 5.14 |
In the 250ml pyrex beaker, use 47%NaOH that the pH of the normal polymkeric substance of 50g is brought up between 8.5 to 9.0.Then this beaker is fixed on the electric furnace that is equipped with thermopair, this thermopair is put in the described beaker, the stainless steel agitator blade that also will be connected in digital agitator is put in the described beaker.Under agitation, 50g distilled water is added described mixture.With the rhodamine 6G of about 0.2g (99%, Aldrich, catalog number (Cat.No.) 25,243-3) be dissolved in ~ 15ml ethanol in.As show shown in the 1C, the ratio of rhodamine 6G and VBC is 0.5/1: 1.It is under agitation also added described mixture.Make the temperature of mixture reach 50 ℃ then, and under agitation under this temperature, kept 23 hours.The Cling film is put into the top of beaker, to avoid evaporating.Then polymkeric substance is cooled off.In order to remove excessive rhodamine 6G, described polymkeric substance is precipitated from the methyl alcohol of its volume of 10x.Under gravity, by being placed on GF/D glass fiber filter paper in the B on the suction lottle, and in distilled water, dissolve again sedimentary polymer filtration.Precipitation is carried out five times.
Table 1C: the ratio of rhodamine 6G and VBC
| The polymkeric substance explanation | Dry (activity) polymer weight/g | VBC weight ( | The VBC mole | Rhodamine 6G weight/g | The rhodamine 6G mole |
| 02/16/A | 50.02 | 0.066 | 4.36× 10 -4 | 0.2 | 4.17× 10 -4 |
| 02/16/C | 50.04 | 7.8×10 -3 | 5.11× 10 -5 | 0.02 | 4.20× 10 -5 |
Embodiment 2: the incrustation scale of preparation mark suppresses multipolymer: the multipolymer of vinylformic acid (AA) and 9-vinyl anthracene (9-VA)
In four necks that are equipped with mechanical stirrer (tetrafluoroethylene blade) and reflux exchanger, 1 liter, the round-bottomed flask that cooperates rapidly, add the 172.5g Urban water supply.With it under agitation, in water-bath, be heated to 90 ℃ with thermopair control.In case container contents reaches temperature, use wriggling and syringe pump respectively, with the solution of the initiator (23% sodium sulfite solution) of 238.4g and chain-transfer agent (CTR), be dissolved in the 11.7g Sodium Persulfate in the 31.4g Urban water supply, with constant rate of speed, in 6 hours, be fed to jointly in the described container.After initiator/CTR charging begins 15 minutes, (15 minutes finish before initiator/CTR charging finishes), use peristaltic pump begin 534.8g vinylformic acid and the 9-vinyl anthracene (97% as indicating among the table 2A with constant rate of speed, in 5.5 hours, Aldrich, catalog number (Cat.No.) V170-8) mix monomer charging, and be fed in the described container.In case polymerization is complete, temperature is brought up to 98 ℃, and container contents was refluxed 2 hours.Then container contents is cooled off.Make N
2Gas passed through described polymers soln bubbling 8 hours, to remove residual SO
2Then with 47%NaOH solution with its pH=5.1-6.1 that neutralizes, and regulate solids content to 53.0-55.0% with Urban water supply.
The final polymer physics performance of AA/9-VA multipolymer is shown in table 2B.
The table 2A:9-VA in the AA multipolymer in conjunction with level
| The polymkeric substance explanation | The gram number of the 9-VA that adds | 9-VA mole % | Suppose and introduce 100% 9-VA, and polymer chain Mw=4000, the amount of chlorine atom of each polymer chain |
| 02/20/A | 1.5 | 0.10 | 1, per 18 polymer chains |
| 02/20/B | 0.75 | 0.05 | 1, per 36 polymer chains |
| 02/20/C | 0.15 | 0.01 | 1, per 183 polymer chains |
The physicals of table 2B:AA/9-VA multipolymer
| The polymkeric substance explanation | Test | ||
| Solids content (0.5g, 130 ℃, 1hr, 3 average)/% | Brookfield viscosity (LV3,30rpm, 25 ℃)/cPs | pH(5％) | |
| 02/20/A (acid) | 63.8 | 4150 | 3.13 |
| 02/20/A | 54.0 | 5690(LV4) | 5.25 |
| 02/20/B (acid) | 65.0 | 3840 | 2.86 |
| 02/20/B | 54.3 | 2090 | 5.25 |
| 02/20/C (acid) | 66.5 | - | 2.53 |
| 02/20/C | 49.6 | - | 5.16 |
Embodiment 3: the incrustation scale inhibition test
The barium sulfate scale of using static bottle examination method to measure the polymkeric substance of all descriptions suppresses usefulness.
With all polymer purifications to remove any unreacted monomer (comprising " mark " monomer).Purifying is to be undertaken by polymers soln is precipitated out from the methyl alcohol of ten times of its volumes.Reclaim sedimentary polymkeric substance by filtering by Whatman filter paper (grade GF/D) under gravity.The polymkeric substance of purifying is dissolved in the water again.Precipitation is carried out 3 times altogether.
Static bottle examination method is used synthetic Forties type local water and North Sea seawater, carries out according to the salt water chemistry among the table 3A.
All salt are weighed in the beaker, and add to distilled water and just to be lower than 1 liter.With solution stirring at least 60 minutes, accurately add to 1 liter with distilled water afterwards.Before using, salt solution is filtered under vacuum by 0.45 micron filter.
Table 3A: salt solution is formed
| Ion | Forties type local water/ppm | North Sea seawater/ppm |
| Na + | 31,275 | 10,890 |
| Ca 2+ | 2,000 | 428 |
| Mg 2+ | 739 | 1,368 |
| K + | 654 | 460 |
| Ba 2+ | 269 | 0 |
| Sr 2+ | 771 | 0 |
| SO 4 2- | 0 | 2,690 |
| Cl - | - | 19,972 |
By 34g sodium acetate 3-hydrate and 0.75g spirit acid are prepared preparation pH=5.5 buffered soln in 250ml distilled water.
Has 3000ppmK by preparation in distilled water
+With the solution of 1000ppm polyvinylsulfonic acid salt, with NaOH solution pH regulator is arrived 8.0-8.5, preparation quencher solution.
The inhibitor stock solution of preparation 1000ppm in seawater.These stock solutions are further diluted, to be given in the seawater 10,20 and the stock solution of 30ppm inhibitor.In duplicate, each of these stock solutions is put into the 100ml Plastic Bottle.In 2 bottles, add 100ml seawater (blank).In other 2 bottles, add 100ml distilled water (contrast).All bottles are put into baking oven one hour under 90 ℃.In the 250ml of equal amount Plastic Bottle, add 100mlForties local water and 2ml buffered soln.These are placed in the water-bath one hour of 90 ℃ of following preheatings.After at this moment, pour the seawater bottle into the local water bottle.All bottles are placed in the water-bath under 90 ℃ again.After 2 and 22 hours, bottle is taken a sample.Draw 1 milliliter of supernatant liquor (noting not disturbance sediment incrustation) with 1 milliliter of whole pipet, and be added in the quencher solution of 9ml preproduction.Barium level in the sample is by inductively coupled plasma spectroscopy (ICP) assay determination.
Inhibitor efficient is represented with percentage ratio:
%BaSO
4Incrustation scale suppresses efficient=(Ba
2+,-Ba
2+ Min)/(Ba
2+ Max-Ba
2+ Min)
Ba
2+ sThe ppm of Ba in the=sample
Ba
2+ MinThe ppm of Ba in=(seawater) blank
Ba
2+ MaxThe ppm of Ba in=(distilled water) contrast
The results are shown in table 3B.
Table 3B: inhibitor barium sulfate suppresses efficient
| Inhibitor | ppm | % efficient | |
| 2 hours | 22 hours | ||
| Poly-(vinylformic acid) | 5 | 34 | 7 |
| 10 | 71 | 21 | |
| 15 | 87 | 24 | |
| Poly-(vinylformic acid/0.1%VBC) | 5 | 42 | 10 |
| 10 | 73 | 24 | |
| 15 | 83 | 15 | |
| Poly-(vinylformic acid/0.1%9-vinyl anthracene) | 5 | 30 | 8 |
| 10 | 52 | 16 | |
| 15 | 81 | 26 |
Embodiment 4: the fluoroscopic examination test
Measure polymer concentration, and 1 and 10ppm between distinguish (differentiated).This tests by (precipitating from methyl alcohol) mass polymer of analyzing purifying.This analysis is the representative of industrial copolymer under the field condition.Herein, unreacted " mark " that is present in the polymkeric substance that is provided will be lost in the stratum.These tests have confirmed the sensitivity (NB:10ppm polymers soln comprise much lower concentration " mark ") of fluorescence analysis for testing goal.They also show the detectability of two kinds of fluorescence " mark " (9-vinyl anthracene and rhodamine 6G).Analysis is carried out in distilled water.
Experimental arrangement
Fluorometric analysis requires to know the maximum excitation (λ of test chemical
EX) and emission (λ
EM) wavelength.9-vinyl anthracene and rhodamine 6G are introduced polymkeric substance, changed its environment and its fluorescence property.So λ
EXAnd λ
EMIntroducing and molar mass distribution with " mark " of polymkeric substance change.For five test polymkeric substance (mass polymer of purifying), maximum λ
EXAnd λ
EMThe use scanning fluorimeter is measured.The λ of five kinds of polymkeric substance
EXAnd λ
EMMaximum value is shown in table 4A.
Table 4A: λ with polymkeric substance of fluorescence " mark "
EXAnd λ
EMMaximum value
| Polymkeric substance | " mark " introduces mole % | Wavelength/nanometer | |
| λ EX | λ EM | ||
| The 02/16/A+ rhodamine 6G | 0.1 | 520.0 | 550.0 |
| The 02/16/C+ rhodamine 6G | 0.01 | 520.0 | 550.0 |
| 02/20/A | 0.1 | 260.0 | 410.0 |
| 02/20/B | 0.05 | 260.0 | 410.0 |
| 20/20/C | 0.01 | 300.0 | 380.0 |
Testing sequence is to be described in those of following document: " pharmaceutical chemical chemical engineering III ", Heriot Watt grade course, experiment 14 " fluorescent quenchings " and FAST handbook.
In the 100ml volumetric flask, be formulated in the 1000ppm inhibitor stock solution in the distilled water.Use 10ml automatic pipette and 100ml volumetric flask,, provide the 100ppm stock solution of 100ml with these stock solutions of distilled water diluting.Use 1ml and 10ml whole pipet further in distilled water, to dilute, provide 0.5,1,2,3,4,5,6,8 and the test soln of 10ppm polymkeric substance.
For every kind of polymers soln, use fixed wave length Perkin-Elmer spectrophotofluorometer 203, in table 4A, describe in detail excite with emission wavelength maximum value under measure emissive porwer.For reading is on the scale, set selector switch and sensitivity according to circumstances.To comprise for each λ
EX/ λ
EMCell (10ppm polymkeric substance) to sample with maximum emission intensity is put into excitation beam, and emissive porwer is set in 100%.The cell that will comprise solvent (distilled water) is put into excitation beam, and emissive porwer is set in 0%.For this λ
EX/ λ
EMRight, do not carry out the correction that further instrumental sensitivity is set up.To have identical λ
EX/ λ
EMThe sample of maximum value is put into excitation beam and is measured emissive porwer.For each new λ
EX/ λ
EMRight, carry out 0%/100% emission absorbancy as mentioned above again and set.
The result
For fluorescence " mark " polymkeric substance of described 5 purifying each, the test soln that comprises 0.5-10ppm is carried out fluorometric assay.The measurement result of the non-fluorescent PAA of these and purifying is compared.
At λ
EX=520nm/ λ
EMThe polymkeric substance that=550nm measures down the results are shown in Fig. 1.These mensuration are that the rhodamine 6G of introducing with 0.01 and 0.1 molecular fraction " mark " is carried out.
At λ
EX=260nm/ λ
EMThe polymkeric substance that=410nm measures down the results are shown in Fig. 2.These mensuration are that the 9-vinyl anthracene of introducing with 0.1 and 0.05 molecular fraction " mark " is carried out.These results clearly illustrate that, two kinds of polymkeric substance all be suitable for 0.5 and 10ppm between polymkeric substance is detected accurately.
At λ
EX=300nm/ λ
EMThe polymkeric substance that=380nm measures down the results are shown in Fig. 3.These mensuration are that the 9-vinyl anthracene of introducing with 0.01 molecular fraction " mark " is carried out.These results show, described polymkeric substance 0.5 and the 10ppm polymkeric substance between can distinguish.
Embodiment 5: for the Clashach sandstone, dynamically core is annotated the research of inhibitor absorption/desorption
Under typical in situ temperature (120 ℃), measured and had and do not had the absorption/desorption form of the polymkeric substance of 9-vinyl anthracene fluorescence " mark " for water saturated sandstone rock core.In addition, because therefore returning to respond by fluorescence and standard quaternary ammonium salt turbidity and monitoring of " mark " polymkeric substance shown between polymkeric substance and " mark " to have stable keyed jointing.
Experimental arrangement
It is existing industrial protocols that core is annotated experiment.The core of selecting that is used for this test is near the Clashach sandstone of appearing of the digging Elgin of Scotland.The core product are cut and are trimmed to has 1.5 inch diameters and 5 inchages.Selected 120 ℃ probe temperature as typical reservoir temperature.Equally according to field practice, inhibitor is infused in refrigerative core under 80 ℃.For these tests, the test salt solution of selection is Forties-type local water and from 50: 50 mixtures of the seawater of the not sulfur-bearing hydrochlorate of embodiment 3.
For " unmarked " of 9-vinyl anthracene and the polymkeric substance of " mark ", core is annotated in identical core notes are equipped with and is carried out abreast, to minimize the variation between the test.Measured the dead volume of annotating two kinds of flow systems in the outfit at described core.Two cores are annotated test, follow following process:
Core preparation and pre-treatment
Core is assembled on the Hassler core print, and it has ~ 2, the confining pressure of 000psi and 180psi (~ 12bar) linear pressure.By toluene was injected described core 15 minutes with the flow of Q=60ml/hr, at room temperature closed described core then 10 minutes, and utilize gentle miscible cleaning thing that two cores are cleaned.This repeats 3/4 time, is clarifying and colourless up to effluent.Repeat this circulation with methyl alcohol then.
By in following current (FF) direction, inject the Forties-type FW of＞20 times of volume of voids with Q=120ml/hr: 50: 50 mixtures of SFSW (filtering the degassing, and pH=5.5), with the salt water saturation of described core.Measure the volume of voids of two cores at room temperature then.After this, in the FF direction, 50: 50 mixtures (filtering the degassing, and pH=5.5) of Forties-type FW: SFSW are injected in the described core, reach 20 times of volume of voids, in this process, be heated 120 ℃ probe temperature with Q=120ml/hr.Described core closed spend the night.Measured brinish pre-treatment rate of permeation under 100% salt water saturation.Under 120 ℃, redeterminate the volume of voids of two cores then.
The application of scale inhibitor
Under 120 ℃, with Q=60ml/hr, the preflush with the SFSW of 3 times of volume of voids in adverse current (RF) direction is injected in two cores.Then described core is cooled to 80 ℃ implantation temperature.After this, under 80 ℃, in the RF direction, 5% main inhibitor treatment agent that will be in SFSW is injected in the described core, reaches 5 times volume of voids with Q=60ml/hr.During the injection stage, constantly monitor differential pressure.Then described core is heated to 120 ℃ and close and spend the night.
Inhibitor discharges and processing back salt solution rate of permeation
Under 120 ℃, in the FF direction, 50: 50 mixtures (filtering the degassing, and the pH=5.5) injection with Forties-type FW: SFSW reaches ~ 1,000 times of pore volume (PV) with Q=60ml/hr.According to following collection effluent sample: 50 * 5ml sample (initial 10PV), 146 * 20ml sample (ensuing 140PV) and for rest part 2 samples every day of post-flush.Measure down at 120 ℃ then and handle back salt solution rate of permeation.
With the described core of 100mol washed with methanol, with displacement salt solution.With core print seat dismounting, and described core is sealed in the cling film preserves.
The result
Figure 4 and 5 have shown the form of returning of the inhibitor that 9-vinyl anthracene " mark " and " unlabelled " polymkeric substance are measured by quaternary ammonium salt analysis (removing salt solution salt carries out).
Fig. 6 and 7 has shown the form of returning of 9-vinyl anthracene " mark " polymkeric substance of measuring by quaternary ammonium salt and fluorometric analysis.
Following table 5 has shown the salt solution changes in permeability before and after the chemical treatment.
Table 5: the core for 9-vinyl anthracene " mark " and " unlabelled " PAA is annotated, the salt solution rate of permeation before and after handling
| Rate of permeation | " unlabelled " PAA | " mark " PAA |
| Under 120 ℃ before the FF direction is handled | 2234 | 3096 |
| Under 120 ℃ before the RF direction is handled | 2520 | 3304 |
| Under 120 ℃ after the FF direction is handled | 2340 | 3096 |
| Under 120 ℃ after the RF direction is handled | 2443 | 2890 |
| Under 120 ℃ at the recovery % of FF direction | 105％ | 93％ |
| Under 120 ℃ at the recovery % of RF direction | 97％ | 94％ |
For 9-vinyl anthracene " mark " and " unlabelled " polymkeric substance, these results demonstrate similar inhibitor and return form.They also demonstrate at the keyed jointing between " mark " and the main polymer chain has stability-allow by fluorescence monitoring " mark " inhibitor during core is annotated.In addition, for 9-vinyl anthracene " mark " or " unlabelled " polymkeric substance, do not see the noticeable change of core salt solution rate of permeation.
Claims (15)
1. the incrustation scale of a mark suppresses polymkeric substance, and it comprises incrustation scale and suppresses unit and indexing unit, and wherein said indexing unit is derived from the monomeric unit 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 heteroatoms, and
-Arom comprises at least two, the group of preferred at least three conjugation aromatic nucleus, and described ring comprises conjugated carbon atom and randomly nitrogen or Sauerstoffatom, and the hydrogen atom or the substituting group that are connected to described carbon atom.
2. the multipolymer of claim 1, wherein said indexing unit is derived from having general formula X
2The monomeric unit of C=CYY ', and wherein Arom is the group that has at least 10 conjugation carbon atoms, preferred at least 14 carbon atoms at least three conjugation aromatic nucleus.
3. the multipolymer of one of aforementioned claim, wherein said conjugation aromatic nucleus is C
5Perhaps C
6Ring.
4. the multipolymer of one of aforementioned claim, wherein Arom is the group with naphthalene, anthracene, pyrene or luxuriant and rich with fragrance part, described part randomly has substituting group.
5. the multipolymer of one of aforementioned claim, wherein L is covalency keyed jointing or divalence C
1-C
12Alkyl group, perhaps have general formula-O-,-CO-O-, CO-NH-,-group of O-CO-.
6. the multipolymer of one of aforementioned claim, wherein said indexing unit are the unit of derived from ethylene base-anthracene, preferred 9-vinyl-anthracene.
7. the multipolymer of one of aforementioned claim, the molar weight of wherein said indexing unit in described multipolymer is 0.01 to 10%.
8. the multipolymer of one of aforementioned claim, 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,
-vinylformic acid, methacrylic acid,
-maleic anhydride, toxilic acid,
-vinylbenzene-p-sulfonic acid, perhaps styrene sulfonate,
-acrylamido-2-methyl propane sulfonic acid (AMPS) and
-its mixture.
9. composition, its incrustation scale that comprises one of aforementioned claim suppresses multipolymer.
10. the composition of claim 9, it is a fluid.
11. the composition of claim 10, wherein said fluid comprise the incrustation scale amount of suppression, the preferred 0.1 described multipolymer to 1000ppm weight.
12. the composition of claim 10 or 11, wherein said fluid are contained in or are intended for to have industrial water system, cooling tower, desalting plant, underground heat power generation, mineral ore extraction, paper pulp manufacturing or the papermaking of boiler.
13. the composition of claim 10 or 11, wherein said fluid are oilfield fluid, preferably water base oil field fluid.
14. the composition of claim 13, wherein said fluid are seawater, local water, recovered water, drilling fluid, well completion fluid, stimulation fluid or squeeze note fluid.
15. one kind prevents or is controlled at and has the method that forms incrustation scale in fluid circulation, the preferred water-based fluid round-robin system, it may further comprise the steps:
-will suppress polymkeric substance at the incrustation scale of the mark of the incrustation scale amount of suppression in the described fluid and add the oil field, perhaps to force the incrustation scale of mark to suppress polymkeric substance and enter the oil field, wherein said fluid will be recycled,
-measure periodically, constantly or continuously the mark in the described fluid amount and
-when observed value was lower than set-point, the incrustation scale that further adds some mark periodically, constantly or continuously suppressed multipolymer, and/or force the incrustation scale inhibition polymkeric substance of described mark to enter described oil field again,
Wherein, described incrustation scale suppresses the incrustation scale inhibition multipolymer that multipolymer is the mark of one of claim 1 to 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48227103P | 2003-06-25 | 2003-06-25 | |
| US60/482,257 | 2003-06-25 | ||
| US60/482,271 | 2003-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1842496A true CN1842496A (en) | 2006-10-04 |
| CN100486914C CN100486914C (en) | 2009-05-13 |
Family
ID=37031104
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800245484A Expired - Fee Related CN100538002C (en) | 2003-06-25 | 2004-06-25 | Use different scale inhibitors to make the method for oilfield stimulation |
| CNB2004800245431A Expired - Lifetime CN100486914C (en) | 2003-06-25 | 2004-06-25 | Tagged scale inhibiting polymers, compositions comprising the same, and method for preventing or controlling scale formation |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800245484A Expired - Fee Related CN100538002C (en) | 2003-06-25 | 2004-06-25 | Use different scale inhibitors to make the method for oilfield stimulation |
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| CN (2) | CN100538002C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054266A (en) * | 2019-05-14 | 2019-07-26 | 济南市坤鹏技术开发中心 | A kind of depth cleaning sewage-treating agent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2665794T3 (en) | 2011-01-19 | 2017-05-22 | Rhodia Operations | FAMILY OF TEMPERATURE INHIBITORS WITH DIFFERENT ABSORPTION PROFILES AND THEIR USE IN OIL FIELDS |
| 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 CNB2004800245484A patent/CN100538002C/en not_active Expired - Fee Related
- 2004-06-25 CN CNB2004800245431A patent/CN100486914C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054266A (en) * | 2019-05-14 | 2019-07-26 | 济南市坤鹏技术开发中心 | A kind of depth cleaning sewage-treating agent |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100486914C (en) | 2009-05-13 |
| CN1846040A (en) | 2006-10-11 |
| CN100538002C (en) | 2009-09-09 |
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