GB2032491A - Well spacer fluids - Google Patents
Well spacer fluids Download PDFInfo
- Publication number
- GB2032491A GB2032491A GB7927760A GB7927760A GB2032491A GB 2032491 A GB2032491 A GB 2032491A GB 7927760 A GB7927760 A GB 7927760A GB 7927760 A GB7927760 A GB 7927760A GB 2032491 A GB2032491 A GB 2032491A
- Authority
- GB
- United Kingdom
- Prior art keywords
- microemulsion
- oil
- surfactant
- weight
- water
- 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.)
- Granted
Links
- 125000006850 spacer group Chemical group 0.000 title claims abstract description 12
- 239000012530 fluid Substances 0.000 title description 2
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 50
- 239000004094 surface-active agent Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003129 oil well Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 235000008206 alpha-amino acids Nutrition 0.000 claims abstract description 6
- 229960003237 betaine Drugs 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 21
- 239000011440 grout Substances 0.000 claims description 12
- -1 aliphatic alcohols Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 claims description 2
- VKGVMRAKNPEFBW-UHFFFAOYSA-M acetyl-dodecyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C(C)=O VKGVMRAKNPEFBW-UHFFFAOYSA-M 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000001455 metallic ions Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 7
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 abstract 1
- 239000004064 cosurfactant Substances 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000002585 base Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 125000003047 N-acetyl group Chemical group 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003940 butylamines Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/424—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells using "spacer" compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/28—Aminocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/26—Oil-in-water emulsions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/26—Oil-in-water emulsions
- C09K8/28—Oil-in-water emulsions containing organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/601—Compositions for stimulating production by acting on the underground formation using spacer compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
Abstract
Microemulsions suitable for use as spacers in oil well cementation comprise a primary surfactant having amphoteric characteristics, one or more cosurfactants, a hydrocarbon and water. The primary surfactant is preferably a betaine or salt of an N- acyl alpha -amino acid. The microemulsions remain effective with water containing considerable quantities of mineral salts. The invention also provides a method cementing oil wells employing such a microemulsion.
Description
SPECIFICATION
Surfactants and microemulsions for use in well cementation
This invention relates to microemulsions containing surfactants and to the cementation of wells, particularly oil wells, using these microemulsions. It has amongst its objects to provide such microemulsions and methods of using them which provide improvements in the quality of cementation of a column in a drilled oil well, when an oil-base slurry is used in the course of the drilling.
In the drilling of an oil well, a slurry is used which, in certain cases, can be an oil-base slurry, which includes emulsions with an aqueous dispersed phase and an oily continuous phase.
When the drilling has reached a suitable level, a column of screwed tubes is dropped and positioned in the well; the well is, of course, filled with slurry. The next operation consists in pumping a grout of cement through the tubes, which are generally filled with slurry, and in discharging the cement grout into the annular space between the column and the walls of the well, and allowing this grout to harden in order to cement this column of tubes to the adjoining ground.
What is sought for in such a cementation is, on the one hand a seal between the various formations in the ground passed through by the well and, on the other hand, anchorage of tubes. It is important, among other things, that the ring of cement should adhere firmly to the walls of the well and to the column of tubes.
If an oil-base slurry is used, the cementation has to take place in the presence of this slurry. Two problems arise, which are linked to the presence of the oil-base slurry. The cement grout and the slurry can mix, forming a magma that is difficult to displace with the techniques applied, and the oil slurry has impregnated and covered the sides of the well which prevents the cement from adhering properly.
These two problems can be solved by the use of a buffer of fluid placed between the slurry and the cement. This buffer, which is known in the oil industry as a "spacer," must have, in order to serve its function as a buffer: (a) a viscosity and density sufficient to keep the slurry and cement from coming in contact with each other, and
(b) characteristics such that it will eliminate, or at least minimise, the oil film deposited on the sides of the hoie by the slurry.
This invention makes it possible to meet these two conditions by the use of certain microemulsions and the controlled use of these microemulsions as "spacers."
The present invention, in one of its aspects, provides a water-oil microemulsion which is suitable for use as a spacer in oil well cementation and which comprises: a primary surfactant having amphoteric characteristics;
one or more co-surfactants;
one or more hydro-carbons; and
water, which may be of variable salinity.
The primary surfactant is generally present in the microemulsions in an amount of from 5 to 25% by weight, from 10 to 20% in the case of an amphoteric surfactant
The co-surfactant(s) is or are generally present in a total amount of form 5 to 25% by weight, more preferably from 10 to 15% by weight.
The hydrocarbon(s) is or are generally present in an amount of from 3 to 80% by weight when an amphoteric primary surfactant is employed and from 20 to 80% by weight when a salt of an N-acyl alpha-amino acid is employed as the primary surfactant.
The water is generally present in an amount of from 20 to 80% by weight and may contain up to 200g/litre of sodium chloride and/or up to 50g/litre of calcium chloride.
The mixture of surfactants may be selected in accordance with the specific properties of the slurry, the cement or the earth in connection with which the microemulsions are to be employed.
The primary surfactant is preferably an amphoteric surfactant but other surfactants having amphoteric characteristics, in particular anionic surfactants having an amphoteric function may be employed as the primary surfactant.
Such a microemulsion, according to a further aspect of this invention is used for the cementation of oil wells which have been drilled with the use of an oil base slurry, by the method which comprises positioning a well casing in the well, injecting microemulsion as defined above to a selected height into the annular space between the well casing and the side of the well, ahead of a cement grout intended for the cementation of the well.
The selection of the said height, which is determined by the volume of microemulsion injected is important and, according to one of the features of this invention the volume injected is that required for it to reach a height of at least 100 metres in the said annular space.
The function of the microemulsion is to reverse the wettability of the walls of the hole by eliminating the oil film and making the grounds wettable with water in order to permit the cement, whose continuous phase is water, to adhere strongly to the formations.
When an amphoteric surfactant is employed as the primary surfactant, it is preferably selected from the group of betaines, and in particular the alkyl di methyl betaines. When there is employed as the primary surfactant an anionic surfactant having an amphoteric function the surfactant is preferably amidic and selected from the group of salts of N-acyl alpha-amino acids.Such surfactants possess the general formula:
wherein R and R' each represent an aliphatic hydrocarbon group, R having from 6 to 32 (preferably 8 to 24) carbon atoms and R' having from 1 to 1 8 carbon atoms, and M represents a metailic cation such as alkali metal ion, an alkaline earth metal ion, an ammonium ion or an amine group which may be primary secondary or tertiary, such as for example methyl-, ethyl-, butyl- or hexylamine, ethylene diamine, diethylene triamine, propylene diamine, hexamethyl diamine, mono-, di or triethanolamine, pyridine, piperidine or piperazine. Particularly preferred surfactants of this general formula are the sodium and potassium N-acetyl alpha-amino alkanoates wherein the alkane has from 8 to 10 carbon atoms.
Examples of the N-acyl alpha-amino acid salts are as follows:
Potassium N-acetyl a-amino caprylate,
Sodium N-butyryl a-amino decanoate,
N-propionyl a-amino dodecanoate of diethylamine,
Sodium N-acetyl a-amino dodecanoate,
Ammonium N-octanoyl a-amino dodecanoate,
Potassium N-acetyl a-amino tetradecanoate,
Pyridinium N-caproyl a-amino tetradecanoate,
di (N-propionyl a-amino hexadecanoate) of ethylene diamine,
Sodium N-acetyl a-amino oleate,
Sodium N-acetyl a-amino octadecanoate,
N-acetyl a-amino linoleate of isobutylamine,
Sodium N-acetyl a-amino tetradecanoate,
Sodium N-oleyl a-amino octadecanoate,
Potassium N-linoleyl a-amino hexanoate.
The reason why the betaines and the N-acyi alpha-amino acid salts are particularly preferred as the primary surfactant of this invention is that they can be utilized together with co-surfactants with water containing as much as 30 to 200g/litre of sodium chloride and up to 50g/litre of calcium chloride.
The or each co-surfactant is preferably selected from short-chain aliphatic alcohols having from 1 to 12 carbon atoms such as, for example, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl alcohols. Other preferred co-surfactants are glycols such as mono-butyl ether of ethylene glycol (B.E.G) and di-butyl ether of ethylene glycol; various ethoxy alcohols; cyclohexanol; methyl cyclohexanol; and benzyl alcohol.
The hydrocarbon or mixture of hydrocarbons may be derived from petroleum products and may be selected from crude oil, fuel-oil and more or less refined fractions of crude oil such as paraffins, olefins, naphthenes, aryl-compounds and other hydrocarbons, as well as those derived from the distillation of oil and from tar, pitch and asphalt.
The following examples give compositions of microemulsions which can be used as "spacers."
The betaine selected in the first two Examples is acetyl dimethyl dodecyl ammonium chloride in the form of a sodium salt, sold under the name of AMPHOSOL DMC/MCA 35. The percentages of
AMPHOSOL refer to the active ingredient of the product which, in the delivered state, contain 35% active ingredient.
EXAMPLE I
We mix, by successive addition and agitation
AMPHOSOL DMC/MCA 35 16.6 % by weight
B.E.G. 1 4 % by weight
Gas-Oil 4.7 % by weight
Salt water saturated with NaCI 64.6 % by weight
EXAMPLE II
AMPHOSOL DMC/MCA 35 15.4 % by weight
B.E.G. 14 % by weight
Gas-Oil 1 5 % by weight
Salt water with 2009 NaCI/I 55.6 % by weight
EXAMPLE Ill
The following microemulsion was prepared by successive addition and agitation:
30.8% by weight of a solution consisting of
Sodium N-acetyl alpha-amino tetradecanoate 40%
Pentanol -1 40% Non-saline water 20 % 48.2% of gas-oil 21% of saturated aqueous NaCI solution
The primary surfactant and the co-surfactant were thus each present in the microemulsion in an amount of 12.3%.
EXAMPLE IT TO VIII
By the procedure of Example Ill but utilizing water containing 200g/litre of sodium chloride, microemulsions were prepared as shown in the following Table 1.
TABLE 1
Example IV V VI VII VIII S.S. 58.1 43.9 28.2 22.6 23.9 S. 23.2 17.6 11,3 9 9.5 G.O. 21.1 34.6 50.2 60 63.1 S.W. 20.8 21.5 21.6 17.4 13 8.8. = Solution of surfactant, % by weight.
S. = Surfactant, % by weight.
G.O. = gas-oil, % by weight.
S.W. = salt water, % by weight.
EXAMPLE IXTO XIV
By following the procedure of Examples lil to VIII but with water containing 50g/litre of sodium chloride and 1 Og/litre of calcium chloride, microemulsions were obtained as shown in the following
Table 2.
TABLE 2
Exampr e IX X IX XII XIII XIV S.S. 53.3 48.7 47 29 30.4 25.3 S. 21.3 19.5 18.8 11.6 12.1 10.1 G.O. 17.5 25.9 26.8 48.6 53.8 61.6 8.W. 29.2 25.4 26.2 22.4 15.8 13.1 These microemulsions have the following characteristics:
density 0.98 to 1.10
apparent viscosity 17 to 20 cp.
plastic viscosity 1 7 to 20 cp.
stability in water containing sodium chloride and calcium chloride
stability at temperatures ranging up to 1000C.
The method of application of the microemulsions according to the invention, as spacers, consists in injecting the microemulsion into the tubes before the cement grout. The necessary volume should be such that the height of the annular space occupied by the spacer will be at least about 1 00 meters.
Thus, in the annular space, the cement grout pushes in front of itself a plug of microemulsion which prepares the surfaces to be cemented.
The efficiency of the application of the microemulsions according to the invention, as spacers, is determined by the extent of the cement-to-ground adhesion. Tests made in the laboratory to determine the efficiency of the microemulsions were conducted as follows:
1) on a sample of earth, of cylindrical shape (diameter 33 mm, height 23 mm), we filtered an oilbase slurry at a differential pressure of 10 kg/cm2 for 1 50 minutes, with agitation at a temperature of 25 to 300 C.
2) the slurry is replaced by the microemulsions; the filtration lasts 20 min. under the same conditions.
3) the microemulsion is replaced by a cement grout; the filtration lasts 30 min. under the same conditions.
4) the sample of earth is placed in a cylindrical mold of 33 mm inner diameter and the face exposed during the filtrations is cemented.
5) after 7 days of hardening of the cement under water, at 25 - 300 C, atmospheric pressure, we unmold and measure the force necessary to break, by shearing, the bond between earth and cement.
The force, reduced to the unit of surface, measures the adhesion of the cement to the earth. It is in the order of:
3 kgf/cm2 when the cement is directly bonded to the earth
1 kgf/cm2 when an oil-base slurry has circulated before the cement grout
3 kgf/cm2 when after oil slurry, Qne of the microemulsions has circulated before the cement grout.
As will be noted, the microemulsions of this invention make it possible to obtain very good
adhesion between a cement grout and a wide variety of earth samples which have undergone the passage of an oil slurry.
Claims (20)
1. A water-oil microemulsion which is suitable for use as a spacer in oil well cementation and
which comprises
a primary surfactant having amphoteric characteristics;
one or more co-surfactants;
one or more hydrocarbons; and water, which may be of variable salinity.
2. A microemulsion according to Claims, wherein the primary surfactant comprises an amphoteric surfactant.
3. A microemulsion according to Claim 2, wherein the amphoteric surfactant comprises a betaine.
4. A microemulsion according to Claim 3, wherein the betaine comprises an alkyl dimethyl
betaine.
5. A microemulsion according to Claim 5, wherein the alkyl dimethyl betaine comprises the sodium salt of acetyl di methyl dodecyl ammonium chloride.
6. A microemulsion according to Claim 1, wherein the primary surfactant comprises an anionic surfactant having amphoteric characteristics.
7. A microemulsion according to Claim 6, wherein the primary surfactant comprises a N-acyl alpha amino acid salt of the following general formula:
wherein R represents an aliphatic hydrocarbon group having from 6 to 32 carbon atoms; R' represents an aliphatic hydrocarbon group having from 1 to 1 8 carbon atoms; and M represents a metallic ion, an ammonium ion or an amine group.
8. A microemulsion according to Claim 7, wherein the primary surfactant comprises a sodium or potassium N-acetyl alpha amino alkanoate wherein the alkane has from 8 to 18 carbon atoms.
9. A microemulsion according to claim 7, wherein the primary surfactant comprises one of the compounds of the general formula defined in Claim 1 and listed hereinbefore.
10. A microemulsion according to any preceding Claim, wherein the co-surfactant(s) is/are selected from short chain aliphatic alcohols having from 1 to 1 2 carbon atoms; glycols and derivatives thereof; ethoxy alcohols; cyclohexanol; methyl cyclohexanol; and benzyl alcohol.
11. A microemulsion according to any preceding Claim, wherein the hydrocarbon comprises gasoil.
12. A microemulsion according to any of Claims 2 to 5, or 10 or 11 when dependent thereupon, which contains
10 to 20% by weight primary surfactant
10 to 15% by weight co-surfactant
3 to 45% by weight hydrocarbon
30 to 80% by weight water/salt solution.
13. A microemulsion according to any of Claims 6 to 9, 10 or 11 when dependent thereupon, which contains:
5 to 25% by weight primary surfactant
5 to 25% by weight co-surfactant
20 to 80% by weight hydrocarbon
20 to 80% by weight water containing up to 200g/litre NaCI and up to 50g/litre CaCI2.
14. A water-oil microemulsion suitable for use as a spacer in oil well cementation, substantially as hereinbefore described with reference to the foregoing Example I or Example II.
1 5. A water-oil microemulsion suitable for use as a spacer in oil well cementation, substantially as hereinbefore described with reference to any one of the foregoing individual Examples Ill to XIV.
1 6. A method of cementing oil wells which have been drilled with the use of an oil base slurry, which comprises positioning a well casing in the well, injecting a microemulsion as defined in claim 1 to a selected height into the annular space between the well casing and the side of the wall, ahead of a grout intended for the cementation of the well.
17. A method according to Claim 16, wherein the volume of microemulsion injected is that required for it to reach a height of at least 100 metres in the said annular space.
18. A method according to claim 1 6 or 17, wherein the microemulsion is as claimed in any one of
Claims 2 to 5, or 10 or 11 when dependent thereupon or in Claim 12.
19. A method according to Claim 1 6 or 17, wherein the microemulsion is as claimed in any one of
Claims 6 to 9 or 10 or 11 when dependent thereupon, or in Claim 13.
20. A method of cementing oil wells, substantially as hereinbefore described.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7832706 | 1978-08-09 | ||
| FR7832005A FR2440773B1 (en) | 1978-11-13 | 1978-11-13 | AQUEOUS MICROEMULSIONS OF ORGANIC SUBSTANCES |
| FR7900180A FR2445854B2 (en) | 1977-07-08 | 1979-01-04 | MICROEMULSIONS FOR USE AS CEMENT "SPACERS" |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2032491A true GB2032491A (en) | 1980-05-08 |
| GB2032491B GB2032491B (en) | 1982-11-10 |
Family
ID=27250870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7927760A Expired GB2032491B (en) | 1978-08-09 | 1979-08-09 | Well spacer fluids |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2032491B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258161B1 (en) * | 1998-11-04 | 2001-07-10 | W. R. Grace & Co.-Conn. | Masonry blocks and masonry concrete admixture for improved freeze-thaw durability |
| WO2010034965A1 (en) * | 2008-09-26 | 2010-04-01 | Halliburton Energy Services, Inc. | Microemulsifiers and methods of making and using same |
| US7906464B2 (en) | 2008-05-13 | 2011-03-15 | Halliburton Energy Services, Inc. | Compositions and methods for the removal of oil-based filtercakes |
| WO2011080506A1 (en) * | 2009-12-30 | 2011-07-07 | Halliburton Energy Services, Inc. | Compressible packer fluids and methods of making and using same |
| WO2022203496A1 (en) * | 2021-03-25 | 2022-09-29 | Chemiservis, S.A. De C.V. | Seawater-based direct emulsion fluid with an inverse oil/water ratio for areas with a low pressure gradient and high temperature |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805154B (en) * | 2014-01-26 | 2016-04-06 | 中国石油天然气股份有限公司 | Carboxybetaine viscoelastic surfactant and the application in tertiary oil recovery thereof |
-
1979
- 1979-08-09 GB GB7927760A patent/GB2032491B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258161B1 (en) * | 1998-11-04 | 2001-07-10 | W. R. Grace & Co.-Conn. | Masonry blocks and masonry concrete admixture for improved freeze-thaw durability |
| US7906464B2 (en) | 2008-05-13 | 2011-03-15 | Halliburton Energy Services, Inc. | Compositions and methods for the removal of oil-based filtercakes |
| WO2010034965A1 (en) * | 2008-09-26 | 2010-04-01 | Halliburton Energy Services, Inc. | Microemulsifiers and methods of making and using same |
| US7833943B2 (en) | 2008-09-26 | 2010-11-16 | Halliburton Energy Services Inc. | Microemulsifiers and methods of making and using same |
| US7960314B2 (en) | 2008-09-26 | 2011-06-14 | Halliburton Energy Services Inc. | Microemulsifiers and methods of making and using same |
| EA021582B1 (en) * | 2008-09-26 | 2015-07-30 | Хэллибертон Энерджи Сервисиз, Инк. | Method for making wellbore servicing fluid and method for wellbore servicing |
| WO2011080506A1 (en) * | 2009-12-30 | 2011-07-07 | Halliburton Energy Services, Inc. | Compressible packer fluids and methods of making and using same |
| US8207096B2 (en) | 2009-12-30 | 2012-06-26 | Halliburton Energy Services Inc. | Compressible packer fluids and methods of making and using same |
| WO2022203496A1 (en) * | 2021-03-25 | 2022-09-29 | Chemiservis, S.A. De C.V. | Seawater-based direct emulsion fluid with an inverse oil/water ratio for areas with a low pressure gradient and high temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2032491B (en) | 1982-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3849316A (en) | Spacer composition | |
| CN103502386B (en) | Viscoelastic fluid of thickening and application thereof | |
| EP0171999B1 (en) | Fluid spacer composition for use in well cementing | |
| US7290615B2 (en) | Fluid having recyclable viscosity | |
| SA01220520B1 (en) | Viscous and elastic surfactants are stable at high concentrations of brine solutions | |
| US4796702A (en) | Multipurpose aqueous foamer | |
| EP3067404B1 (en) | Methods for use in oil and/or gas wells | |
| US3850248A (en) | Method of using a spacer fluid for spacing drilling muds and cement | |
| RU2453576C2 (en) | High temperature lubricating agent for updating viscosity of low- and high-density brines | |
| RU2724060C2 (en) | Ultra-high-viscosity tampons and methods of their use in drilling system of oil wells | |
| US5110487A (en) | Enhanced oil recovery method using surfactant compositions for improved oil mobility | |
| US2946746A (en) | Oil-external emulsion drilling fluids | |
| EA031823B1 (en) | Wellbore servicing compositions and methods of making and using same | |
| MXPA06013660A (en) | Subterranean fluids and methods of cementing in subterranean formations. | |
| MX2012000471A (en) | Emulsion stabilizing agents for drilling and completion fluids. | |
| US4474240A (en) | Drilling fluid displacement process | |
| RU2770200C2 (en) | Compositions for increasing oil recovery | |
| US4223732A (en) | Microemulsions for use as spaces in well cementation | |
| CA2906165A1 (en) | Methods and compositions for use in oil and/or gas wells | |
| US3663477A (en) | Dilatant aqueous polymer solutions | |
| US4588031A (en) | Well cementing process | |
| US5282984A (en) | Generating bitumen-in-water dispersions and emulsions | |
| GB2032491A (en) | Well spacer fluids | |
| EP0159837B1 (en) | Stimulation of oil and gas wells with phosphate ester surfactants | |
| EA009065B1 (en) | Delayed phase changing agent for invert emulsion drilling fluid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920809 |