CA1177634A - Invert emulsions for well-drilling comprising a polydiorganosiloxane and method therefor - Google Patents
Invert emulsions for well-drilling comprising a polydiorganosiloxane and method thereforInfo
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- CA1177634A CA1177634A CA000392106A CA392106A CA1177634A CA 1177634 A CA1177634 A CA 1177634A CA 000392106 A CA000392106 A CA 000392106A CA 392106 A CA392106 A CA 392106A CA 1177634 A CA1177634 A CA 1177634A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- 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
- C09K23/54—Silicon compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/922—Fracture fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/925—Completion or workover fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/926—Packer fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/927—Well cleaning fluid
- Y10S507/928—Spacing slug or preflush fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/935—Enhanced oil recovery
Abstract
INVERT EMULSIONS FOR WELL-DRILLING COMPRISING
A POLYDIORGANOSILOXANE AND METHOD THEREFOR
ABSTRACT OF THE DISCLOSURE
The preparation of emulsions of light and heavy brines in a liquid hydrocarbon is described, using a polydiorganosiloxane bearing at least one polyoxyalkylene radical and at least one monovalent hydrocarbon radical having from 6 to 18 carbon atoms.
The emulsions are useful in the well-drilling art as drilling fluids, completion fluids, packer fluids, spacer fluids and workover fluids because of their thermal stability and because they can be formulated to have a relatively high density, with or without added weighting agents.
A POLYDIORGANOSILOXANE AND METHOD THEREFOR
ABSTRACT OF THE DISCLOSURE
The preparation of emulsions of light and heavy brines in a liquid hydrocarbon is described, using a polydiorganosiloxane bearing at least one polyoxyalkylene radical and at least one monovalent hydrocarbon radical having from 6 to 18 carbon atoms.
The emulsions are useful in the well-drilling art as drilling fluids, completion fluids, packer fluids, spacer fluids and workover fluids because of their thermal stability and because they can be formulated to have a relatively high density, with or without added weighting agents.
Description
`~ 17'~634 INVE~T ~i~ULSIONS FOR WELL-DRILLING COMPRISING
A POLYDI~GANOSIL~XANE AN~ METH~ T~EFO~
The present invention relatea to invert emulsions for the ~ell-drilliny industry and to a method for their preparation. More particularly, the present invention relates to compositions comprisiny an emulsion of a brine in a li~uid hydrocar~on whicl~
are useful in well-drilliny operations, such as in ~as- and/or oil-well drilliny, as a drilliny fluid, a completion fluid, a worKover fluia, a casiny pack fluid, a fracturing fluid, a packer fluid and a spacer fluid.
Invert emulsions, in the form of drilling muds, completion fluids and packer fluids are well known in t~le well-drillin~ art. Invert emulsions typically consist of a fluid phase comprisiny from 15 to 45 percent by volume of a CaCl2 brine, and 55 to 85 percent by volume of diesel oil and a solid phase comprisiny ayents for pressure control, filtration control, viscosity control, gelling, etc. An invert emulsion drilliny mud ~enerally contains from 5 to 30 percent by volume of the brine.
While conventional invert emulsions are used in drilliny deep welis, where hiyh temperature anà
pressure are commonly encountered, they are not .. ' ~
, completely satisfactory for such a use. ~'or example, invert emulsiorls are sometimes not suf~iciently stable at tne l~lyh temperatures encountered in dee~ wells.
Furthermore, the use of excessive amounts of a wei~htin~ agent in an invert emulsion to achieve pressure controi in deep we~ls is often undesiraole because performance and properties of the emulsion can be adversly affected. Ileavier brlnes, such as CaBr~
brines and/or Zn~r~ ~rines, ~lave been used to increase tlle density of an invert emulsion, thereby achieviny ~reater pressure control, however, sometimes the t~lermal stability of these heavier emulsions is marginal or non-existent. Further improvements i~
pressure control and in temperature stability of tne invert emulsion are needed.
~rief SummarY of the Invention It is an object of this invention to provide a solids-free invert emulsion which is suitable for use in the well-drilliny industry. It is another ob~ect of this invention to provide invert emulsions of a niyh density brine wnich have stability at hiyh telnperature. It is a furtner ob~ect of tnis invention to ~rovide im~roved invert emulsion muds. It is another ob~ect of this invention to provide :
soiids-free invert emulsions haviny hiyh density and ~einy suita~le for use in a deep-well drilliny. It is also an ob~ect of this invention to provide a method for yrepariny the invert emulsions of this invention.
It is yet another ob~ect of this invention to provide a yolydioryanosiloxane/liquid hydrocarbon concentrate which is useful for yrepariny improved invert emulsions.
-' ~1~7'7~4 These ob]ects, and others, wnicn will become o~vious when consideriny the ~ollowiny ~i~closure and appended claims, are obtained by the present invention wnicrl comprises emulsifyilly a ~rlne in a ii~uid hydrocarbon containiny certain polydiorganosiloxane surface active ayents. Accordiny to this invention it is possible not only to prepare a thermally sta~le emulsion of a niyh density brine but also to prepare a stable emulsion comprisiny a fluid phase haviny a ma~or amount of a i~igh density brine and a minor amount of a liquid hydrocarbon. The resultiny invert emulsions are sufficiently dense to permit their use as a soli~s-free completion fluid in deep well drilliny; they can also be formulated to contain solid and/or li~uid components whic~l are commonly used in the well-drilliny art for various purposes, such as for prepariny invert emulsion drilliny muds.
Detailed Description of the Invention Tne present invention relates to an emulsion composition to be used in well-drilling and comprisiny (A) from 1 to 7~ parts by volume of a brine as a discontinuous p~as`e, (B) from 25 to ~ parts by volume of a li~uid nydrocarbon selected from the yroup consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, yas oil and paraffins haviny a flash yoint of at least 10~F as a continuous phase, and (C) from 0.05 to 15 parts by weiyht, for every 100 parts by weiyht of brine plus liquid hydrocarbon, of a polydioryanosiloxane haviny the formula '' ~ .
'7~, ~;3~
Z3~iOL(C~ 2SiO~X~(Ctl3)(R)SiO~y~ 13)(~)~iO~ ;iZ~
wherein U denotes a polyoxyalkylene radical haviny the formula -~'(OCli~CH~)p(OC~2C~C~3)~0~ denot~q a monovalent hydrocarbon radical haviny from 6 to 18 car~on atoms, inclusive, R' ~enotes a divalent radical ~onded to a silicon atom by a silicon-carbon ~ond, ~"
denotes a monovalent ra~ical selected from the yroup consistiny of hydrogen~ alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, Z denotes a monovalent nydrocarbon radical haviny from 1 to 5 carbon atoms, inclusive, or an R radlcal or a ~ radical, x has an averaye value of from 0 to 400, y has an averaye value of from 0 to 4V~, z has an averaye value of from U to 5, x + ~ + z has an average value of from 30 to 400, p nas an averaye value e~ual to or greater than tne averaye value of ~ and ~ + ~ has an averaye value sufficient to provide a formula weight of from ~U0 to 3500 for the -(OCH2CH2)p(0CH~CHCH3)~- portion of the radical, there being an averaye of at least one ~
radical and an averaye of at least one R radical per nolecule of the polydiorganosiloxane.
Tne present invention furtner relates to a method for prepariny the emulsion compositions of this invention comprisiny (I) mixing, to form a solution, (i) 0.5 to 15 parts by weiyht of a polydioryano-siloxane haviny the formula Z~sio[(c~3)2sio~xi(c~3)(R)SiOly[(c~3)(Q)~io~z~iz3 wherein ~ denotes a polyoxyalkylene radical haviny tne forrnula -R'(OC~2CH2)p(0CH2CHC~3)~0R", ~ denotes a ` i~7763~
monovalent hydrocarbon radical haviny an averaye of from 6 to 18 carbon atoms, inclusive, ~' denotes a divalent radical ~onded to a silicon atom by a silicon-carbon bond, ~" denotes a monovalent radical selected from the group consistiny of ~Iydroyen~ alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, ~
denotes a luonovalent hydrocarboll radical haviny from 1 to 5 carbon atoms, inclusive, or an ~ radical or a radical, x nas an averaye value of from 0 to ~0U, y has an averaye value of from 0 to 400, z has an averaye value of from U to ~, x + ~ + z has an averaye value of from 3~ to ~U0, ~ has an averaye value equal to or greater tnan the averaye value of ~ and ~ + q has an averdye value sufficient to ~rovide a formula weight of from 60U to 3500 for the -(OCH2CH~)p(OC~CHCH3)~- portion of the ~ radical, t~lere beiny an averaye of at least one Q radical and an averaye of at least one R radical per molecule of the polydioryanosiloxane, and (ii) aV parts by vol~ne Ol a liquid hydrocarbon selected from the yrouy consistiny of kero~ene, diesel oil, crude oil, turbine fuel, mineral oil, yas oil and paraffins naviny a flasll ~Oillt of at least lUUF, (II) mixiny the - solution of ste~ (I) with bV parts by volume of tne liquid nydrocarbon, (III) mixiny V' part ~y volume of a brine Witil the solution of step (II) with sufficient shear eneryy to provide an emulsion haviny a brine particle size of less than 10 micrometers in diameter, ,..
. .
11'7'7~
and (IV~ mixin~ the emulsion of itep (III) with cV
parts ~y volwne of the liquid hydrocarbon, wherein V
~las an averaye of rrom ~5 to ~ parts hy volurne, a ~as d vaiue of frolll yreater than ~ero to 1, ~ has a value of from ~ero to 1ess t~lan l, c has a value of froln zero to less than 1, a plus b plus c has a value of 1, V' has a value of from 1 to 75 parts r~y volume and the weiyht of V plus V' llas a value of 100 ~arts by weiynt.
The present invention further relates to a polydioryanosiloxane/liquid hydrocarbon concentrate comprisiny from ~.~ to 15 parts by weiyht of the polydioryanosiloxane component and a portion of the liquld hydrocarbon equal to from 0.0001 to 0.1 of the total amount of liquid hydrocarbon component that is used to prepare the emulsiol- coMpositions oL this invention.
T~e discontinuous phase of the emulsion compositions of this invention is a brine. ~erein, the term brine is used in its ~roadest sense, i.e. an aqueous solution of a salt containiny at least 3 percent ~y weiyht of the salt. Prefera~ly the brine is a saturated aqueous solution of the salt at ~0C.
The term ~rine further includes brine occuriny naturally or brine prepare~ synthetically. It is within the scope and spirit of this invention to dissolve one or more salts in natural brine to prepare a brine suita~le for use in the compositions of this invention.
- . .
~7'7~
The salt portion of the brine ~referably ha4 a lli9h solubility in water at room tem~erature so tllat the emulsion compositions of this invention can be formulated to have a wide ranye of densities. The salt advantayeously has, in addition to a hiyh solubility in water, a lar~e formula wei~ht so that tne brine can be formulated to have a hiyh density, for exaïnple up to 22 pounds per ~allon (2642 kiloyrams per cubic meter).
Salts typically used in the well-drilliny art, and beiny suitable for use in tne compositions of this inventiorl, include sodium chloride, sodium carbonate, potassium chloride, potassi~n carbonate, calcium chloride, calcium bromide, zinc chloride, zinc bromide and mixtures thereof.
~ onveniently, a suita~le brine for the compositions of this invention can be the natural brine that is frequently present at the drilliny site where t~lese compositions are used. In this case the yresent invention contemplates the storiny of the other components of tnese compositions, hereinafter delineated, at the driiling site as separate and/or mixed components and formulating the emulsions of this invention in-the-field, as desired. Said natural brine can be further mixed with a salt, lf aesire~.
-`` 11'7'~
; A preferred brine in the emulsioll compositions of this invention comprises water saturated with a Inixture of calcium bromide and zinc bromide and haviny a density of about ~ pound~ per yallon at ~C. Such a brine can be emulsified in a li~uid hydrocarbon accordiny to this invention to provide an emulsion that needs no additional weiyhtiny ayent, such as barium sulfate, to permit its use as a completion fluid in petroleum- and/or yas-well driliings. Said emulsion can also be readily formulated with well-known additives to provide improved drilling muds for deep petrole~n- and/or yas-weil drillings.
Tne continuous phase of the emulsion compositions of this invention is a liquid hydrocarbon selected from tne yroup consistiny of ~araffins having a flash point of at least lU~F, kerosene, turbine fuel, crude oil, diesel oil, gas oil, mineral oil and mixtures thereof.
Conveniently and economically, tne li~uid nydrocdrbon can be the crude oil that is beiny recovered from, and/or the hydrocarbon fuel suc~ as diesel fuel, that is being used at, the drilling site where the compositions of thls invention are used.
~hen additional factors beyond convenience and economics, such as safety, handliny and environmental factors, are considered, mineral oil can ~e advantayeously used as the li~uid hydrocarbon in the compositions of this invention because of its ., ~, , ~ .
:` ' ' - 11'7'7~
g relatively low volatility and relatively low odor. In any case the polydioryanosiloxane, delineated below, can ~e conveniently stored at the drilliny field as a neat component, or as a concentrate in a li~uid hydrocarbon if desired, and the compositions of this invention prepared therefrom in-the-field as desired.
The polydioryanosiloxane component of the compositions of this invention has the formula Z3~i~L(C~3)~Si~x[(C~3)(~)SiO~yL(C~3)(~)siO~zsiz3. (I
In formula (I) each R denotes, independently, a silicon-bonded -Inonovalent hydrocarbon radical having from ~ to l~ carbon atoms, both inclusive, such as strai~ht-chained or branched-chain alkyl radicals, such as hexyl, lleptyl, octyl, nonyl, decyl, undecyl, do~ecyl, tetradecyl, llexadecyl and octadecyl;
cycloaliphatic radicals, such as cyclo~lexyl; aryl radica1s, SUCll as phenylr tolyl, xenyl and naphthyl;
and arylalkyi radicals, such as benzyl, 2-phenylethyl and 2-phenylpropyl. Preferably, R denotes an al~yl radical having from 6 to 18 carbon atoms, such as the octyl, decyl or dodecyl radical, to provide easy solu~ility of the polydior~anosiloxane in t~le liquid hydrocarbon of the compositions of this invention.
Form~la (I) can contain all the same R radicals or mixtures of two or more R radicals, as deslred.
,:, , ., ,~, , ,, .
:
....
.
.. ' `` 11'7~
-lU-In formula (I) each ~ denotes, inde~endently, a silicon-bonde~ polyoxyalkylene radical llaving the formula -K'(OC~C~)p(OC~2CHCH3)qORI'. (II) In the formula (II), R' denotes a divalent radical which bonds the polyoxyalkylene radical to a silicon atom by way of a silicon-car~on ~ond to provide hydrolytic stability therefor. The COMpOsitiOn of the ~' radical is not critical as long as it does not undergo nydrolytic cleavaye in the com~ositions of this invention. Ty~ically, R' is an alkylene radical, sucn as -C~2CH2-, -C~C~2CH~- or -CH~CH~C~(CH3)-.
In fonnula (II) R" denotes a monovalent radical selected from the yroup consistiny of the hydroyen atom; an alkyl radical, such as methyl, ethyl~ propyl and ~utyl; an aryl radical, such as phenyl or tolyl; an arylalkyl radical, such as benzyl;
or an acyl radical, such as acetyl. The composition of the ~" ra~ical is not critical; however, it is prefera~ly a small radical such as the methyl radical or the acetyl radical and, most ~referably, the nydrogen atom.
~ - , ' .
.1177~
In formula ~II), p and ~ denote numbers whose sum is sufficient to provide an averaye formula wei~ht of from ~UO to 35UU for the -~OCH~C~2)~(0C~2C~C~3)~-portion of the U radical and the value of ~ is e~ual to or yreater than tne value of ~. ~hat is to say, t~le ratio of the number of oxypropylene units to the number of oxyet~lylene units in the ~ radical has a value e~ual to or less than 1, such as U, U.l, 0.~, 0.5 and 1Ø In a preferred embodiment of this invention the sum of p + ~ has a value of about SU.
In formula (I) Z denotes a monovalent hydrocar~on radical havin~ from 1 to 5 carbon atoms, inclusive, or a ~ radical, or an R radical, as hereina~ove delineated. Tne composition of the Z
radical is not critical except wnen the values of y and/or z in the formula (I) are/is zero, in whicn case a sufficient number of Z radicals must be said R
radical and/or Q radical, so that the polydioryanosiloxane contains, per molecule, an averaye of at least one R radical and an averaye of at least one Q radical. Typical radicals contemplated as Z radicals, in addition to said R and Q radicals delineated above, include methyl, ethyl, propyl, isopropyl and vinyl. Preferably all Z radicals are methyl radicals.
~;
., .'' :;
` ' `: ~
..~, ~.:, . .. .
,:, , 1177~
.~
In formula ~I) x denotes d number llavin~ an averaye value of from 0 to 400, preferably from 0 to 100; y denotes a number haviny an averaye value of from 0 to 40~, preferably from 1 to 10~; and z denotes a number having an average value of from 0 to 5, preferably from 1 to 5; wit~lin the further re~uirement tllat the sum of x + ~ + z has a value of from 30 to ~, preferably from 30 to ~0.
The polydior~anosiloxane can also contain small ~nounts of unreacted precursor silicon-~onded radicals, such as llydroyen radicals, or chloroalkyl radicals which were present in the precursor materials that was used to prepare the polydioryanosiloxane, and trace amounts of incidental silicon-bonded radicals, suc~l as hydroxyl radicals or alkoxy radicals wnich were incidentally introduced into the molecule duriny preparation of tne polydioryanosiloxane.
~refera~ly there are no precursor radicals and incidental radicals in the polydioryanosiloxane.
A first preferred polydioryanosiloxane in the compositions of this invention hdS the formula ~ C~3)3Sio[(C~3)(R)SiO~y[(C~3~(Q)SiO]zSi(C~3)3 (Ia) where1n the averaye values of y and z are yreater than ~ero and their sum has a value of from 30 to 7U. A
,. . .
' ;' ' `~.. .
.
: .
.
-, 77~
-13- ;~
higl~ly preferred polydioryanosiloxane haviny the formula (Ia) is o~tained when ~ denotes an alkyl radical and ~ denotes a polyoxyalkylene radical ~aving the formula -CH~CH2CH~(OC~C~p(OC~2CH~H3)~0~ (IIa) wherein the sum of ~ + ~ has a value of aDout 50; i.e.
as an averaye value of from about ~5 to 50 and q has an averaye value of from about 0 to 25.
A second preferred polydiorganosiloxane in the compositions of this invention has the formula (c~)3sio[(c~3)~sio~x[(cH3)(R)SiO]y[(c~3)(~)sio]zsi-(CH~)3 (Ib) wherein x has an averaye value of about 100, y has an averaye value of from about 30 to 70 and z has an averaye value of from 1 to 5. A hiyhly preferred polydiorganosiloxane having the formula (Ib) is obtained when R and Q are as noted above for the first hiyhly preferred polydiorganosiloxane component.
The polydioryanosiloxane component may ~e prepared by any suitable method; several are disclosed in the organosilicon art. A preferred method for preparing tne polydioryanosiloxane component comprises reactiny a metnyl siloxane having terminal and/or in-the-chain silicon-bonded hydroyen radicals with .
)~:
,~
' ,: . -. :
' ~ .
-11'7'7~
an olefin haviny from 6 to 1~ carbon atoms, SUCtl as l-dodecene and an olefinically terminated l~olyoxy-alkylene, such as ~2=C~CH~(OCH~C~2)p(OC~C~CH3)~O~ in the presence of a platinum-containiny catalyst, such as H~PtC16 ~O. In this preferred method the olefin and the olefinically terminated polyoxyalkylene are most preferably reacted seyuentially with the methylsiloxane containing silicon-bonded hydrogen radicals. The disclosures of U.S. Patent Nos.
3,657,305; 3,234,252; 4,047,958; 3,427,271 and
A POLYDI~GANOSIL~XANE AN~ METH~ T~EFO~
The present invention relatea to invert emulsions for the ~ell-drilliny industry and to a method for their preparation. More particularly, the present invention relates to compositions comprisiny an emulsion of a brine in a li~uid hydrocar~on whicl~
are useful in well-drilliny operations, such as in ~as- and/or oil-well drilliny, as a drilliny fluid, a completion fluid, a worKover fluia, a casiny pack fluid, a fracturing fluid, a packer fluid and a spacer fluid.
Invert emulsions, in the form of drilling muds, completion fluids and packer fluids are well known in t~le well-drillin~ art. Invert emulsions typically consist of a fluid phase comprisiny from 15 to 45 percent by volume of a CaCl2 brine, and 55 to 85 percent by volume of diesel oil and a solid phase comprisiny ayents for pressure control, filtration control, viscosity control, gelling, etc. An invert emulsion drilliny mud ~enerally contains from 5 to 30 percent by volume of the brine.
While conventional invert emulsions are used in drilliny deep welis, where hiyh temperature anà
pressure are commonly encountered, they are not .. ' ~
, completely satisfactory for such a use. ~'or example, invert emulsiorls are sometimes not suf~iciently stable at tne l~lyh temperatures encountered in dee~ wells.
Furthermore, the use of excessive amounts of a wei~htin~ agent in an invert emulsion to achieve pressure controi in deep we~ls is often undesiraole because performance and properties of the emulsion can be adversly affected. Ileavier brlnes, such as CaBr~
brines and/or Zn~r~ ~rines, ~lave been used to increase tlle density of an invert emulsion, thereby achieviny ~reater pressure control, however, sometimes the t~lermal stability of these heavier emulsions is marginal or non-existent. Further improvements i~
pressure control and in temperature stability of tne invert emulsion are needed.
~rief SummarY of the Invention It is an object of this invention to provide a solids-free invert emulsion which is suitable for use in the well-drilliny industry. It is another ob~ect of this invention to provide invert emulsions of a niyh density brine wnich have stability at hiyh telnperature. It is a furtner ob~ect of tnis invention to ~rovide im~roved invert emulsion muds. It is another ob~ect of this invention to provide :
soiids-free invert emulsions haviny hiyh density and ~einy suita~le for use in a deep-well drilliny. It is also an ob~ect of this invention to provide a method for yrepariny the invert emulsions of this invention.
It is yet another ob~ect of this invention to provide a yolydioryanosiloxane/liquid hydrocarbon concentrate which is useful for yrepariny improved invert emulsions.
-' ~1~7'7~4 These ob]ects, and others, wnicn will become o~vious when consideriny the ~ollowiny ~i~closure and appended claims, are obtained by the present invention wnicrl comprises emulsifyilly a ~rlne in a ii~uid hydrocarbon containiny certain polydiorganosiloxane surface active ayents. Accordiny to this invention it is possible not only to prepare a thermally sta~le emulsion of a niyh density brine but also to prepare a stable emulsion comprisiny a fluid phase haviny a ma~or amount of a i~igh density brine and a minor amount of a liquid hydrocarbon. The resultiny invert emulsions are sufficiently dense to permit their use as a soli~s-free completion fluid in deep well drilliny; they can also be formulated to contain solid and/or li~uid components whic~l are commonly used in the well-drilliny art for various purposes, such as for prepariny invert emulsion drilliny muds.
Detailed Description of the Invention Tne present invention relates to an emulsion composition to be used in well-drilling and comprisiny (A) from 1 to 7~ parts by volume of a brine as a discontinuous p~as`e, (B) from 25 to ~ parts by volume of a li~uid nydrocarbon selected from the yroup consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, yas oil and paraffins haviny a flash yoint of at least 10~F as a continuous phase, and (C) from 0.05 to 15 parts by weiyht, for every 100 parts by weiyht of brine plus liquid hydrocarbon, of a polydioryanosiloxane haviny the formula '' ~ .
'7~, ~;3~
Z3~iOL(C~ 2SiO~X~(Ctl3)(R)SiO~y~ 13)(~)~iO~ ;iZ~
wherein U denotes a polyoxyalkylene radical haviny the formula -~'(OCli~CH~)p(OC~2C~C~3)~0~ denot~q a monovalent hydrocarbon radical haviny from 6 to 18 car~on atoms, inclusive, R' ~enotes a divalent radical ~onded to a silicon atom by a silicon-carbon ~ond, ~"
denotes a monovalent ra~ical selected from the yroup consistiny of hydrogen~ alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, Z denotes a monovalent nydrocarbon radical haviny from 1 to 5 carbon atoms, inclusive, or an R radlcal or a ~ radical, x has an averaye value of from 0 to 400, y has an averaye value of from 0 to 4V~, z has an averaye value of from U to 5, x + ~ + z has an average value of from 30 to 400, p nas an averaye value e~ual to or greater than tne averaye value of ~ and ~ + ~ has an averaye value sufficient to provide a formula weight of from ~U0 to 3500 for the -(OCH2CH2)p(0CH~CHCH3)~- portion of the radical, there being an averaye of at least one ~
radical and an averaye of at least one R radical per nolecule of the polydiorganosiloxane.
Tne present invention furtner relates to a method for prepariny the emulsion compositions of this invention comprisiny (I) mixing, to form a solution, (i) 0.5 to 15 parts by weiyht of a polydioryano-siloxane haviny the formula Z~sio[(c~3)2sio~xi(c~3)(R)SiOly[(c~3)(Q)~io~z~iz3 wherein ~ denotes a polyoxyalkylene radical haviny tne forrnula -R'(OC~2CH2)p(0CH2CHC~3)~0R", ~ denotes a ` i~7763~
monovalent hydrocarbon radical haviny an averaye of from 6 to 18 carbon atoms, inclusive, ~' denotes a divalent radical ~onded to a silicon atom by a silicon-carbon bond, ~" denotes a monovalent radical selected from the group consistiny of ~Iydroyen~ alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, ~
denotes a luonovalent hydrocarboll radical haviny from 1 to 5 carbon atoms, inclusive, or an ~ radical or a radical, x nas an averaye value of from 0 to ~0U, y has an averaye value of from 0 to 400, z has an averaye value of from U to ~, x + ~ + z has an averaye value of from 3~ to ~U0, ~ has an averaye value equal to or greater tnan the averaye value of ~ and ~ + q has an averdye value sufficient to ~rovide a formula weight of from 60U to 3500 for the -(OCH2CH~)p(OC~CHCH3)~- portion of the ~ radical, t~lere beiny an averaye of at least one Q radical and an averaye of at least one R radical per molecule of the polydioryanosiloxane, and (ii) aV parts by vol~ne Ol a liquid hydrocarbon selected from the yrouy consistiny of kero~ene, diesel oil, crude oil, turbine fuel, mineral oil, yas oil and paraffins naviny a flasll ~Oillt of at least lUUF, (II) mixiny the - solution of ste~ (I) with bV parts by volume of tne liquid nydrocarbon, (III) mixiny V' part ~y volume of a brine Witil the solution of step (II) with sufficient shear eneryy to provide an emulsion haviny a brine particle size of less than 10 micrometers in diameter, ,..
. .
11'7'7~
and (IV~ mixin~ the emulsion of itep (III) with cV
parts ~y volwne of the liquid hydrocarbon, wherein V
~las an averaye of rrom ~5 to ~ parts hy volurne, a ~as d vaiue of frolll yreater than ~ero to 1, ~ has a value of from ~ero to 1ess t~lan l, c has a value of froln zero to less than 1, a plus b plus c has a value of 1, V' has a value of from 1 to 75 parts r~y volume and the weiyht of V plus V' llas a value of 100 ~arts by weiynt.
The present invention further relates to a polydioryanosiloxane/liquid hydrocarbon concentrate comprisiny from ~.~ to 15 parts by weiyht of the polydioryanosiloxane component and a portion of the liquld hydrocarbon equal to from 0.0001 to 0.1 of the total amount of liquid hydrocarbon component that is used to prepare the emulsiol- coMpositions oL this invention.
T~e discontinuous phase of the emulsion compositions of this invention is a brine. ~erein, the term brine is used in its ~roadest sense, i.e. an aqueous solution of a salt containiny at least 3 percent ~y weiyht of the salt. Prefera~ly the brine is a saturated aqueous solution of the salt at ~0C.
The term ~rine further includes brine occuriny naturally or brine prepare~ synthetically. It is within the scope and spirit of this invention to dissolve one or more salts in natural brine to prepare a brine suita~le for use in the compositions of this invention.
- . .
~7'7~
The salt portion of the brine ~referably ha4 a lli9h solubility in water at room tem~erature so tllat the emulsion compositions of this invention can be formulated to have a wide ranye of densities. The salt advantayeously has, in addition to a hiyh solubility in water, a lar~e formula wei~ht so that tne brine can be formulated to have a hiyh density, for exaïnple up to 22 pounds per ~allon (2642 kiloyrams per cubic meter).
Salts typically used in the well-drilliny art, and beiny suitable for use in tne compositions of this inventiorl, include sodium chloride, sodium carbonate, potassium chloride, potassi~n carbonate, calcium chloride, calcium bromide, zinc chloride, zinc bromide and mixtures thereof.
~ onveniently, a suita~le brine for the compositions of this invention can be the natural brine that is frequently present at the drilliny site where t~lese compositions are used. In this case the yresent invention contemplates the storiny of the other components of tnese compositions, hereinafter delineated, at the driiling site as separate and/or mixed components and formulating the emulsions of this invention in-the-field, as desired. Said natural brine can be further mixed with a salt, lf aesire~.
-`` 11'7'~
; A preferred brine in the emulsioll compositions of this invention comprises water saturated with a Inixture of calcium bromide and zinc bromide and haviny a density of about ~ pound~ per yallon at ~C. Such a brine can be emulsified in a li~uid hydrocarbon accordiny to this invention to provide an emulsion that needs no additional weiyhtiny ayent, such as barium sulfate, to permit its use as a completion fluid in petroleum- and/or yas-well driliings. Said emulsion can also be readily formulated with well-known additives to provide improved drilling muds for deep petrole~n- and/or yas-weil drillings.
Tne continuous phase of the emulsion compositions of this invention is a liquid hydrocarbon selected from tne yroup consistiny of ~araffins having a flash point of at least lU~F, kerosene, turbine fuel, crude oil, diesel oil, gas oil, mineral oil and mixtures thereof.
Conveniently and economically, tne li~uid nydrocdrbon can be the crude oil that is beiny recovered from, and/or the hydrocarbon fuel suc~ as diesel fuel, that is being used at, the drilling site where the compositions of thls invention are used.
~hen additional factors beyond convenience and economics, such as safety, handliny and environmental factors, are considered, mineral oil can ~e advantayeously used as the li~uid hydrocarbon in the compositions of this invention because of its ., ~, , ~ .
:` ' ' - 11'7'7~
g relatively low volatility and relatively low odor. In any case the polydioryanosiloxane, delineated below, can ~e conveniently stored at the drilliny field as a neat component, or as a concentrate in a li~uid hydrocarbon if desired, and the compositions of this invention prepared therefrom in-the-field as desired.
The polydioryanosiloxane component of the compositions of this invention has the formula Z3~i~L(C~3)~Si~x[(C~3)(~)SiO~yL(C~3)(~)siO~zsiz3. (I
In formula (I) each R denotes, independently, a silicon-bonded -Inonovalent hydrocarbon radical having from ~ to l~ carbon atoms, both inclusive, such as strai~ht-chained or branched-chain alkyl radicals, such as hexyl, lleptyl, octyl, nonyl, decyl, undecyl, do~ecyl, tetradecyl, llexadecyl and octadecyl;
cycloaliphatic radicals, such as cyclo~lexyl; aryl radica1s, SUCll as phenylr tolyl, xenyl and naphthyl;
and arylalkyi radicals, such as benzyl, 2-phenylethyl and 2-phenylpropyl. Preferably, R denotes an al~yl radical having from 6 to 18 carbon atoms, such as the octyl, decyl or dodecyl radical, to provide easy solu~ility of the polydior~anosiloxane in t~le liquid hydrocarbon of the compositions of this invention.
Form~la (I) can contain all the same R radicals or mixtures of two or more R radicals, as deslred.
,:, , ., ,~, , ,, .
:
....
.
.. ' `` 11'7~
-lU-In formula (I) each ~ denotes, inde~endently, a silicon-bonde~ polyoxyalkylene radical llaving the formula -K'(OC~C~)p(OC~2CHCH3)qORI'. (II) In the formula (II), R' denotes a divalent radical which bonds the polyoxyalkylene radical to a silicon atom by way of a silicon-car~on ~ond to provide hydrolytic stability therefor. The COMpOsitiOn of the ~' radical is not critical as long as it does not undergo nydrolytic cleavaye in the com~ositions of this invention. Ty~ically, R' is an alkylene radical, sucn as -C~2CH2-, -C~C~2CH~- or -CH~CH~C~(CH3)-.
In fonnula (II) R" denotes a monovalent radical selected from the yroup consistiny of the hydroyen atom; an alkyl radical, such as methyl, ethyl~ propyl and ~utyl; an aryl radical, such as phenyl or tolyl; an arylalkyl radical, such as benzyl;
or an acyl radical, such as acetyl. The composition of the ~" ra~ical is not critical; however, it is prefera~ly a small radical such as the methyl radical or the acetyl radical and, most ~referably, the nydrogen atom.
~ - , ' .
.1177~
In formula ~II), p and ~ denote numbers whose sum is sufficient to provide an averaye formula wei~ht of from ~UO to 35UU for the -~OCH~C~2)~(0C~2C~C~3)~-portion of the U radical and the value of ~ is e~ual to or yreater than tne value of ~. ~hat is to say, t~le ratio of the number of oxypropylene units to the number of oxyet~lylene units in the ~ radical has a value e~ual to or less than 1, such as U, U.l, 0.~, 0.5 and 1Ø In a preferred embodiment of this invention the sum of p + ~ has a value of about SU.
In formula (I) Z denotes a monovalent hydrocar~on radical havin~ from 1 to 5 carbon atoms, inclusive, or a ~ radical, or an R radical, as hereina~ove delineated. Tne composition of the Z
radical is not critical except wnen the values of y and/or z in the formula (I) are/is zero, in whicn case a sufficient number of Z radicals must be said R
radical and/or Q radical, so that the polydioryanosiloxane contains, per molecule, an averaye of at least one R radical and an averaye of at least one Q radical. Typical radicals contemplated as Z radicals, in addition to said R and Q radicals delineated above, include methyl, ethyl, propyl, isopropyl and vinyl. Preferably all Z radicals are methyl radicals.
~;
., .'' :;
` ' `: ~
..~, ~.:, . .. .
,:, , 1177~
.~
In formula ~I) x denotes d number llavin~ an averaye value of from 0 to 400, preferably from 0 to 100; y denotes a number haviny an averaye value of from 0 to 40~, preferably from 1 to 10~; and z denotes a number having an average value of from 0 to 5, preferably from 1 to 5; wit~lin the further re~uirement tllat the sum of x + ~ + z has a value of from 30 to ~, preferably from 30 to ~0.
The polydior~anosiloxane can also contain small ~nounts of unreacted precursor silicon-~onded radicals, such as llydroyen radicals, or chloroalkyl radicals which were present in the precursor materials that was used to prepare the polydioryanosiloxane, and trace amounts of incidental silicon-bonded radicals, suc~l as hydroxyl radicals or alkoxy radicals wnich were incidentally introduced into the molecule duriny preparation of tne polydioryanosiloxane.
~refera~ly there are no precursor radicals and incidental radicals in the polydioryanosiloxane.
A first preferred polydioryanosiloxane in the compositions of this invention hdS the formula ~ C~3)3Sio[(C~3)(R)SiO~y[(C~3~(Q)SiO]zSi(C~3)3 (Ia) where1n the averaye values of y and z are yreater than ~ero and their sum has a value of from 30 to 7U. A
,. . .
' ;' ' `~.. .
.
: .
.
-, 77~
-13- ;~
higl~ly preferred polydioryanosiloxane haviny the formula (Ia) is o~tained when ~ denotes an alkyl radical and ~ denotes a polyoxyalkylene radical ~aving the formula -CH~CH2CH~(OC~C~p(OC~2CH~H3)~0~ (IIa) wherein the sum of ~ + ~ has a value of aDout 50; i.e.
as an averaye value of from about ~5 to 50 and q has an averaye value of from about 0 to 25.
A second preferred polydiorganosiloxane in the compositions of this invention has the formula (c~)3sio[(c~3)~sio~x[(cH3)(R)SiO]y[(c~3)(~)sio]zsi-(CH~)3 (Ib) wherein x has an averaye value of about 100, y has an averaye value of from about 30 to 70 and z has an averaye value of from 1 to 5. A hiyhly preferred polydiorganosiloxane having the formula (Ib) is obtained when R and Q are as noted above for the first hiyhly preferred polydiorganosiloxane component.
The polydioryanosiloxane component may ~e prepared by any suitable method; several are disclosed in the organosilicon art. A preferred method for preparing tne polydioryanosiloxane component comprises reactiny a metnyl siloxane having terminal and/or in-the-chain silicon-bonded hydroyen radicals with .
)~:
,~
' ,: . -. :
' ~ .
-11'7'7~
an olefin haviny from 6 to 1~ carbon atoms, SUCtl as l-dodecene and an olefinically terminated l~olyoxy-alkylene, such as ~2=C~CH~(OCH~C~2)p(OC~C~CH3)~O~ in the presence of a platinum-containiny catalyst, such as H~PtC16 ~O. In this preferred method the olefin and the olefinically terminated polyoxyalkylene are most preferably reacted seyuentially with the methylsiloxane containing silicon-bonded hydrogen radicals. The disclosures of U.S. Patent Nos.
3,657,305; 3,234,252; 4,047,958; 3,427,271 and
2,84~,4S~ show methods for prepariny the polydioryanosiloxane component of the compositions of tiliS invention.
i~any ~olydioryanosiloxanes suitable for use in the compositions of this invention are viscous uids or waxy soli~s and are conveniently prepared and used as a solution in a suita~le solvent such as the li~uid nydrocarbon component hereinabove delineated.
The emulsion compositions of this invention can comprise from 1 to 75, preferably 10 to 60, parts by volume of the brine component and from 25 to ~9, preferably 40 to 90, parts by volume of the li~uid hydrocar~on component, tne most preferred amounts dependiny upon the particular brine that is used, the particular li~uid hydrocarbon thdt is use~ and the .
';' ' 1i;~7763~
-lS-.
particular use of the emulsion composition in the well-drillin~ art. For example, when a solids-free completion fluid emulsion of this invention is to be used to urevent blOW-OUt, i.e. the uncontrolled release of well-pressure, it is preferred that the emulsion composition comprise a maximutn volume of a brine having a maximum density without destabilizing the emulsion to breaking lphase separation) or to inversion (phase reversal). A highly preferred emulsion composition of this invention for preventin~
blow-out thus comprises from 40 to ~0 parts by volume of a saturated a~ueous solution of Ca~r~ and ZnBr2 haviny a density of about 2U pounds per gallon.
The amount of uolydioryanosiloxane to be used in the emulsion compositions of this invention is ~ased on the total wei~ht of the brine and liquid hydrocarbon and can ranye from 0.5 to 15, preferably to 6 parts by welght for every 10U parts by weiyht of brine plus li~uid hydrocarbon. The proper amount of polydioryanosiloxane to be used in any particular emulsion will depend upon the particular brine and liquid hydrocarbon that is used and their relative volumes and can be determined by simple exyerimentation, in view of the examples hereinafter disclosed.
., , .
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.. ~ ' .
1177~
The emulsion compositions of t~lis invention can be ~re~ared by conventional emulsifyiny methods.
~referably the polydiorganosiloxane is dissolved in : all, or a ~ortion, of the li~uid nydrocarbon com~onent to form a solution and the brine component is thereafter emulsified therein wit~l sufficient shear energy to provide an emulsion haviny a ~rine particle size of less than 10, preferably less than 1, microJneter in diameter, any remaining liquid hydrocarbon being mixed with said emulsion.
~ pecifically, from 0.5 to 15 parts by weiyht of tne polydiorganosiloxane is first dissoived in aV
parts by volulne of the liquid hydrocarbon where a denotes a number having a value of from yreater than zero to 1 and V has a value of from 25 to 99 parts by volume. When a nas a vaiue of 1, V' ~arts by volurne of the ~rine are emulsified in the solution of polydiorgarlosiloxane in liquid hydrocarbon, where V' has a value of from 1 to 75 ~arts by volume and the total weight of V + V' has a value of 100 parts by weiyht, to ~rovide the emulsion com~ositions of t~lis invention.
In a preferred emvodiment of this invention a has a value of less than 1, such as from O.OUOl to O.l, to provide a concentrateo solution of tne .~ .
.
li'~7~3'~
polydior~anosiloxane which is ship~ed and/or stored and is subse~uently used to form the compositions of this invention. In tnis case the concentrate is Yu~se~uen~ly uilute~ with bV parts ~y volume of the liquld hydrocar~on where b denotes a number of from zero to less than one, preferably (l-a). When _ has a ` value of (l-a), V' parts by volume of the brine are emulsified in the diluted concentrated solution of polydioryanosiloxane in liquid hydrocarbon, where V' has a value of from 1 to 75 parts by volume and the total of V + V' nas a value of lOU parts by weiyht, to provide the emulsion compositions of this invention.
In a variation of the preferred embodiment of thls invention b has a value of less than (l-a), preferably yreater than zero. In this case V' parts by volume of the brine are emulsified in the solution of polydioryanosiloxane in liquid hydrocar~on and cV
parts by volume of the liquid hydrocarbon are added to the resulting emulsion, where c has a value of (l-a-b), V' ~as a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight, to provide the emulsion composition of this invention.
In the method of this invention the liquid hydrocarbon that is used in each step of emulsion formatioll may be the same or different. It is prefeFred that the polydior~anosiloxane component be :;
. ,~ , , .
~i'7'7~
dissolved in from ~.~OOlV to O.lV ~arts by volume of a paraffin hydrocarbon haviny a flash point of at least 1~Fj`and the remaininy portion of li~uid llydrocarbon that is used to form the emulsion be diesel fuel an~/or crude oil.
The method and compositions of tnis invention further comprises the use of an oryanic, non-ionic surfactant in sufficient amount to reduce the interfacial tension between ti~e brine component and the solution of polydioryanosiloxane in li~uid nydrocarbon component without destabiliziny the emulsion. A~vantageously, the use of an oryanic, non-ionic surfactant allows the emulsion composition of this invention to be pre~ared under greatly reduced shear energy so that they can be prepared with simple paddle mixiny instead of turbine mixing, homoyenizer mixiny or colloid mixing. This aspect of the invention finds great utility when the compositions of this invention are prepared in-the-field. In the method of this invention any oryanic, non-ionic surfactant may be incorporated at any time up to and duriny the emulsifyiny ~rocess. Preferably any organic, non-ionic surfactant is mixed with the solution of polydioryanosiloxane in li~uid hydrocarbon ~efore the ~rine component is emulsified therein.
Conveniently any oryanic, non-ionic surfactant can ~e mixed with the concentrate of polydiorganosiloxane in li~uid hydrocarbon in the preferred metho~ of this invention.
~ ' .
li'7'7fai;~
~ .
The preferred oryanic, non-ionic surfactant to ~e used in the method and compositions o~ t~-is invention will depend upon the compositioll of the brine component. For example, a nonylphenoxypoly-ethoxyethanol haviny approximately three oxyethylene units per molecule has ~een found to be an effective surfactant for reduciny needed shear eneryy when used . witll liyht ~rines, such as a 30 percent by weight solution of CaC12 in water. For heavier brines, comprising CaBr2 and/or ZnBr~ a long-chain alkanol, such as hexanol, octanol or decanol has been found to ~e an effective surfactant. Preferably the organic, ;j~ non-ionic surfactant has a hydrophile-lipophile balance (H.L.B.) value of from 2 to 10.
~ The amount of oryanic, non-ionic surfactant i to be used in the method of this invention is l yenerally equal to from ~.5 to 1.5 times the amount of polydioryanosiloxane component that is used in any ;~ particular composition.
An ef~ective ~nount and type of organic, ;` non-ionic surfactant to be used for any specific combination of ~rine and liquid hydrocar~on can be simply deterlnined, in view of the followiny exaluples and well-known co-surfactant technology, by performiny ' a ~ew routine experiment~. A suitable procedure :
:
:, 11; 7~ 4 comprises incorporatiny a few cosurfactant candidate materials at a few concentrations in a series of comuositiorls of this invention, ayitatiny the mixture with paddle mixing to thorouyhly disæerse the brine in the li~uid hydrocarbon and allowiny the resulting mixture to stand at room temuerature for 24 hours. A
com~osition of this invention haviny an effective amount and type of oryanic non-ionic surfactant will not separate duriny the ~4 hour observation period.
Tne compositions of this invention can comprise any of the additives which are generally dissolved or suspended in invert emulsions of the art to modify emulsion properties such as viscosity, filtration, yelliny, density and lubricity. ~xamples of said additives include weiyhtiny ayents, such as ~arium sulfate, oyster shells, yalena, iron oxide, or uowdered limestone; filtration control agents, such as colloidal Cldys and oxidi~ed asuhalts; and viscosity control ayents, such as alkaline-neutralized fatty acids, rosin acids and tall oil and uolymer fluids, such as xanthan gums, hydroxycellulose and polyacrylamide .
The followin~ examples are disclosed to further teach i~ow to make and use the present invention.
' .
~ ` "
11','7f~
Example 1 Six parts Dy weiyht of a trlmethylsiloxy-endsto~ped polydioryanosiloxane consistiny of about 64 (cH3)lc8~l7)sio2/2 siloxalle units and about 1 (cH3)(Ho(cH~cH2o)~4(c~2c~c~3~)24 CH~CH2CH2)Sio~/~ siloxane unit per molecule was dissolved in 34 parts ~y weiyht (41.5 parts by volume) of die6el fuel. The resultiny solution was ayitated in a ~alnilton ~each malt r~lixer and a brine consisting of 15 parts by weiyht (8.~ parts by volume) of an aqueous solution of CaBr~ and 45 parts ~y weiyht (19.6 parts by volume) of an aqueous solution of CaBr~ and ZnBr~ was slowly added tnereto. The mixture was .stirred until the brine particles had a diameter of less than 1 micrometer. A brine-in-llquid hydrocarbon emulsion was obtained which had a viscosity of 2~0 centi~oise at 25C and which did not separate when exposed to a temperature of 350F for lb hours in a pressurized, stainless steel Baroid~ hiyh temperature ayiny cell.
~xample ~
T~ree ~arts by weiyht of a trimethylsiloxy--endstopped polydioryanosiloxane consistiny of about lOU (C~3)~Sio2/~ siloxane units, about 45 (CH3)(Cl~s)Sio~/2 siloxane units and about 2.5 (CH3)(HO(C~C~2O)~4(C~2C~CH3O)~4c~2c~c~2)sio2/~
siloxane units per molecule was dissolved in 34.5 parts by weight (45 parts by volume) of Stoddard :
"
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.
-7~3~
~;~
solvent 'rhe resultiny solution was ayitated in an ~ppenbach tur~ine stirrer and 11~.1 uarts ~y weiyht (5~ parts ~y volume) of an a~ueous solution of Ca~r~
and '~n~r2 was slowly added t~lereto. The resulting ~rine-in-li~uid hydrocarbon etnulsion had a brine particle size of from 5 to 7 micrometers and, after standiny at room temperature for ~ weeks, ex~erienced about lS percent by volume settliny.
Example 3 Exam~le 2 was repeated with the exception that 3 parts ~y weight of a non-ionic surfactant (nonylphenoxy~olyethoxy(4)et~lanol) was also dissolved in the li~uid llydrocarbon before the brine was emulsifiea therein. 'rhe resultin~ brine-in-li~uid nydrocarbon elnulsion was thicker than the emulsion of Example 2, had a particle size of less tnan 5 nicrometers an~ experiences about 7 to 1~ percent settling after ~ wee~s at room temperature. When this example was repeated without the polydioryanosiloxane, a stable emulsion was not obtained.
Example 4 Four parts Dy weiyht of a polydioryano-siloxane haviny the formula (cH3)3sioL(cH3) 2SiOlXL(Cfl3)(~)SiO]yL(Ctl3)(51)~zSi(CH3)3 wllerein x has a value of about 100, y has a value of about ;
, I
;~
....
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., ,~; `
1.1'~"7~
4S, ~ has a value of about ~.5, ~ denotes the dodecyl radical and ~ denotes the -C~c~2c~2(oc~2c~2)~(oc~c~c~c~3~OH
radical wherein p and ~ each have a value of about 24 was mixed with 1 part by weight (1.7 parts by volume) of an isoparaffin haviny a flash point of at least 10UF (Isopar~ M) to form a concentrate solution.
This concentrate, and ~ parts by weiyht of ethoxylated tridecylalcohol (Tergitol~ 15-S-3) were dissolved in 32 parts ~y welyht (39 parts by volume) of fuel oil ~2, usiny a paddle mlxer. The paddle mixer was rotated at 4U~ to 5U0 r.p.m. and 6~ parts by weiyht (4b. ~ parts ~y volume) of a 3~ percent by weiyht solution of CaCl~ in water was slowly added to the stirred solution. ~fter the brine had been completely adde~ the mixture was stirred for 30 minutes and a stable (at ieast ~ weeks) brine-in-fuel oil emulsion was obtained which had a particle size of less than 1 microlneter. This emulsion could `~e further diluted wit~l fuel oil ~2.
Exam~le 5 Example 4 was reyeated except that the ~rine was thickened with hydroxyethylcellulose before it was emulsified in the fuel-oil. An emulsion haviny a smaller particle size and a ~reater sta~ility than that of the emulsion of Example 4 was obtained.
,~
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' . . .
.
ill'7~7~ai3~
-~4-~xample 6 Four parts by weiyht of the polydioryanosiloxane use~ in Example 4 was mixed witn 1 part by weiyht (1.3 parts ~y volume) of Isopar~ M.
Tl~e resultiny concentrated solution, and 3 parts by wei~ht of dodecanol, were mixed with 33 parts by weiynt (~0.2 parts by volume) of diesel fuel using a three-bladed paddle mixer. The mixer was rotated at 4UU to 50u r.p.m. and 6~ parts by weight (26 parts by volume) of a ~rine containing ZnBr2 and CaBr~ was slowly added to the stirred solution. A thixotropic emulsion havin~ a brine particle size of less than U.5 micrometer and a stability of at least seven days at room temperature was o~tained. When this low-shear metilod was repeated in tne absence of dodecanol the resulting emulsion separated within 24 l~ours.
Exam~le 7 Example 6 was repeated except an identical alnount or decanol, instead of dodecanol, was used.
rhe resultlny emulsion was stable, but not ~uite as stable as the emulsion of Example 6.
Example 8 ~ xample 7 was repeated except that an identical weiyht of Alaska crude oil, instead of diesel fuel, was used. The resulting emulsion of neavy brine-in-li~uid hydrocar~on had an averaye particle si~e of less than 1 micrometer and was stable to separation for at least 7 days.
., ., . .
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~xample ~
About 4.5 parts ~y weight of the po'ydioryanosiloxane described in Example 4 was dissolved in 46.5 parts by weiyht (56.7 parts by volume) of diesel fuel #2. The resulting solution was placed in an Eppenbach mixer and agitated while 41.
parts ~y weiyht (1~.2 parts by volume~ of the heavy ~rine described in ~xample 6 (sold by ttle ~ow Chemical Compally~ as ~W-V) was slowly emulsified therein. The resultiny emulsion was thickened ~y addiny 7.2 parts ~y weiynt of an amille-treated bentonite clay (~entone~
~). The resultin~ composition of this invention ~ad an averaye particle size of less than 1 micrometer.
A portion of the thickened emulsion was placed in each of 5 stainless steel ayiny vessels, the vessels were pressurized with nitroyen and then sealed. One vessel was heated at 3~F for 5 days, after which tlle averaye particle size was no more than 2 micrometers. Another vessel was heated at 400E` for 7 days with similar results. Another vessel was heated at 500F for 5 days witn substantially identical results. Anotner vessel was heated at 600F
for ~ days with similar results. The remainin~ vessel was l~eated at 700~ for 5 days, after which some deyraded naterial was noted but the averaye particle size did not exceed ~ micrometers. T~lis example illustrates the thermal stability of a drilliny fluid composition of tnis invention.
.
';J6;3~
--;~b--Example 10 Four parts by weiyht of the polydiorganosiloxane described in Example 4 was dissolved in 31 parts by weiyht (37.~ parts by vol~ne) o~ diesel fuel #2. ~rhe resultiny solution was placed in an ~ppen~ac~l mixer and ayitated whiie bO parts by weiyht (26 parts by volume) of the heavy brine descrived in Example 6 and S parts ~y weiynt of t~le bentonite clay descri~ed in Example 9 were slowly added, se~uentially, thereto. Tne resultiny emulsion had an average brine particle size of no more than 1 micrometer. The thermal sta~ility of t~le emulsion at 5~0F for 5 days was evaluated as described in Example Y. The averaye particle size of the neated emulsion did not exceed ~ micrometers, with a few particles beiny as large as 5 micrometers.
Example 11 The polydioryanosiloxane described in ~xample ,- 1.6 ~arts by weight, was dissolved in 78 parts by weiyht (95.i parts by volume) of diesel fuel ~. The resultiny solution was placed in an Eppenbacn mixer and stirred while 14 parts by weiyht (10.8 parts by volume) of a liyht CaCl~ brine was slowly added thereto. The resulting emulsion was further thickened witn 6 parts ~y weight of an amine-treated bentonite clay (~entone~ 3~). The resultiny emulslon had an averaye brine particle si~e of frorl 0.3 to ~.5 micrometer.
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i~any ~olydioryanosiloxanes suitable for use in the compositions of this invention are viscous uids or waxy soli~s and are conveniently prepared and used as a solution in a suita~le solvent such as the li~uid nydrocarbon component hereinabove delineated.
The emulsion compositions of this invention can comprise from 1 to 75, preferably 10 to 60, parts by volume of the brine component and from 25 to ~9, preferably 40 to 90, parts by volume of the li~uid hydrocar~on component, tne most preferred amounts dependiny upon the particular brine that is used, the particular li~uid hydrocarbon thdt is use~ and the .
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particular use of the emulsion composition in the well-drillin~ art. For example, when a solids-free completion fluid emulsion of this invention is to be used to urevent blOW-OUt, i.e. the uncontrolled release of well-pressure, it is preferred that the emulsion composition comprise a maximutn volume of a brine having a maximum density without destabilizing the emulsion to breaking lphase separation) or to inversion (phase reversal). A highly preferred emulsion composition of this invention for preventin~
blow-out thus comprises from 40 to ~0 parts by volume of a saturated a~ueous solution of Ca~r~ and ZnBr2 haviny a density of about 2U pounds per gallon.
The amount of uolydioryanosiloxane to be used in the emulsion compositions of this invention is ~ased on the total wei~ht of the brine and liquid hydrocarbon and can ranye from 0.5 to 15, preferably to 6 parts by welght for every 10U parts by weiyht of brine plus li~uid hydrocarbon. The proper amount of polydioryanosiloxane to be used in any particular emulsion will depend upon the particular brine and liquid hydrocarbon that is used and their relative volumes and can be determined by simple exyerimentation, in view of the examples hereinafter disclosed.
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The emulsion compositions of t~lis invention can be ~re~ared by conventional emulsifyiny methods.
~referably the polydiorganosiloxane is dissolved in : all, or a ~ortion, of the li~uid nydrocarbon com~onent to form a solution and the brine component is thereafter emulsified therein wit~l sufficient shear energy to provide an emulsion haviny a ~rine particle size of less than 10, preferably less than 1, microJneter in diameter, any remaining liquid hydrocarbon being mixed with said emulsion.
~ pecifically, from 0.5 to 15 parts by weiyht of tne polydiorganosiloxane is first dissoived in aV
parts by volulne of the liquid hydrocarbon where a denotes a number having a value of from yreater than zero to 1 and V has a value of from 25 to 99 parts by volume. When a nas a vaiue of 1, V' ~arts by volurne of the ~rine are emulsified in the solution of polydiorgarlosiloxane in liquid hydrocarbon, where V' has a value of from 1 to 75 ~arts by volume and the total weight of V + V' has a value of 100 parts by weiyht, to ~rovide the emulsion com~ositions of t~lis invention.
In a preferred emvodiment of this invention a has a value of less than 1, such as from O.OUOl to O.l, to provide a concentrateo solution of tne .~ .
.
li'~7~3'~
polydior~anosiloxane which is ship~ed and/or stored and is subse~uently used to form the compositions of this invention. In tnis case the concentrate is Yu~se~uen~ly uilute~ with bV parts ~y volume of the liquld hydrocar~on where b denotes a number of from zero to less than one, preferably (l-a). When _ has a ` value of (l-a), V' parts by volume of the brine are emulsified in the diluted concentrated solution of polydioryanosiloxane in liquid hydrocarbon, where V' has a value of from 1 to 75 parts by volume and the total of V + V' nas a value of lOU parts by weiyht, to provide the emulsion compositions of this invention.
In a variation of the preferred embodiment of thls invention b has a value of less than (l-a), preferably yreater than zero. In this case V' parts by volume of the brine are emulsified in the solution of polydioryanosiloxane in liquid hydrocar~on and cV
parts by volume of the liquid hydrocarbon are added to the resulting emulsion, where c has a value of (l-a-b), V' ~as a value of from 1 to 75 parts by volume and the weight of V + V' has a value of 100 parts by weight, to provide the emulsion composition of this invention.
In the method of this invention the liquid hydrocarbon that is used in each step of emulsion formatioll may be the same or different. It is prefeFred that the polydior~anosiloxane component be :;
. ,~ , , .
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dissolved in from ~.~OOlV to O.lV ~arts by volume of a paraffin hydrocarbon haviny a flash point of at least 1~Fj`and the remaininy portion of li~uid llydrocarbon that is used to form the emulsion be diesel fuel an~/or crude oil.
The method and compositions of tnis invention further comprises the use of an oryanic, non-ionic surfactant in sufficient amount to reduce the interfacial tension between ti~e brine component and the solution of polydioryanosiloxane in li~uid nydrocarbon component without destabiliziny the emulsion. A~vantageously, the use of an oryanic, non-ionic surfactant allows the emulsion composition of this invention to be pre~ared under greatly reduced shear energy so that they can be prepared with simple paddle mixiny instead of turbine mixing, homoyenizer mixiny or colloid mixing. This aspect of the invention finds great utility when the compositions of this invention are prepared in-the-field. In the method of this invention any oryanic, non-ionic surfactant may be incorporated at any time up to and duriny the emulsifyiny ~rocess. Preferably any organic, non-ionic surfactant is mixed with the solution of polydioryanosiloxane in li~uid hydrocarbon ~efore the ~rine component is emulsified therein.
Conveniently any oryanic, non-ionic surfactant can ~e mixed with the concentrate of polydiorganosiloxane in li~uid hydrocarbon in the preferred metho~ of this invention.
~ ' .
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The preferred oryanic, non-ionic surfactant to ~e used in the method and compositions o~ t~-is invention will depend upon the compositioll of the brine component. For example, a nonylphenoxypoly-ethoxyethanol haviny approximately three oxyethylene units per molecule has ~een found to be an effective surfactant for reduciny needed shear eneryy when used . witll liyht ~rines, such as a 30 percent by weight solution of CaC12 in water. For heavier brines, comprising CaBr2 and/or ZnBr~ a long-chain alkanol, such as hexanol, octanol or decanol has been found to ~e an effective surfactant. Preferably the organic, ;j~ non-ionic surfactant has a hydrophile-lipophile balance (H.L.B.) value of from 2 to 10.
~ The amount of oryanic, non-ionic surfactant i to be used in the method of this invention is l yenerally equal to from ~.5 to 1.5 times the amount of polydioryanosiloxane component that is used in any ;~ particular composition.
An ef~ective ~nount and type of organic, ;` non-ionic surfactant to be used for any specific combination of ~rine and liquid hydrocar~on can be simply deterlnined, in view of the followiny exaluples and well-known co-surfactant technology, by performiny ' a ~ew routine experiment~. A suitable procedure :
:
:, 11; 7~ 4 comprises incorporatiny a few cosurfactant candidate materials at a few concentrations in a series of comuositiorls of this invention, ayitatiny the mixture with paddle mixing to thorouyhly disæerse the brine in the li~uid hydrocarbon and allowiny the resulting mixture to stand at room temuerature for 24 hours. A
com~osition of this invention haviny an effective amount and type of oryanic non-ionic surfactant will not separate duriny the ~4 hour observation period.
Tne compositions of this invention can comprise any of the additives which are generally dissolved or suspended in invert emulsions of the art to modify emulsion properties such as viscosity, filtration, yelliny, density and lubricity. ~xamples of said additives include weiyhtiny ayents, such as ~arium sulfate, oyster shells, yalena, iron oxide, or uowdered limestone; filtration control agents, such as colloidal Cldys and oxidi~ed asuhalts; and viscosity control ayents, such as alkaline-neutralized fatty acids, rosin acids and tall oil and uolymer fluids, such as xanthan gums, hydroxycellulose and polyacrylamide .
The followin~ examples are disclosed to further teach i~ow to make and use the present invention.
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Example 1 Six parts Dy weiyht of a trlmethylsiloxy-endsto~ped polydioryanosiloxane consistiny of about 64 (cH3)lc8~l7)sio2/2 siloxalle units and about 1 (cH3)(Ho(cH~cH2o)~4(c~2c~c~3~)24 CH~CH2CH2)Sio~/~ siloxane unit per molecule was dissolved in 34 parts ~y weiyht (41.5 parts by volume) of die6el fuel. The resultiny solution was ayitated in a ~alnilton ~each malt r~lixer and a brine consisting of 15 parts by weiyht (8.~ parts by volume) of an aqueous solution of CaBr~ and 45 parts ~y weiyht (19.6 parts by volume) of an aqueous solution of CaBr~ and ZnBr~ was slowly added tnereto. The mixture was .stirred until the brine particles had a diameter of less than 1 micrometer. A brine-in-llquid hydrocarbon emulsion was obtained which had a viscosity of 2~0 centi~oise at 25C and which did not separate when exposed to a temperature of 350F for lb hours in a pressurized, stainless steel Baroid~ hiyh temperature ayiny cell.
~xample ~
T~ree ~arts by weiyht of a trimethylsiloxy--endstopped polydioryanosiloxane consistiny of about lOU (C~3)~Sio2/~ siloxane units, about 45 (CH3)(Cl~s)Sio~/2 siloxane units and about 2.5 (CH3)(HO(C~C~2O)~4(C~2C~CH3O)~4c~2c~c~2)sio2/~
siloxane units per molecule was dissolved in 34.5 parts by weight (45 parts by volume) of Stoddard :
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solvent 'rhe resultiny solution was ayitated in an ~ppenbach tur~ine stirrer and 11~.1 uarts ~y weiyht (5~ parts ~y volume) of an a~ueous solution of Ca~r~
and '~n~r2 was slowly added t~lereto. The resulting ~rine-in-li~uid hydrocarbon etnulsion had a brine particle size of from 5 to 7 micrometers and, after standiny at room temperature for ~ weeks, ex~erienced about lS percent by volume settliny.
Example 3 Exam~le 2 was repeated with the exception that 3 parts ~y weight of a non-ionic surfactant (nonylphenoxy~olyethoxy(4)et~lanol) was also dissolved in the li~uid llydrocarbon before the brine was emulsifiea therein. 'rhe resultin~ brine-in-li~uid nydrocarbon elnulsion was thicker than the emulsion of Example 2, had a particle size of less tnan 5 nicrometers an~ experiences about 7 to 1~ percent settling after ~ wee~s at room temperature. When this example was repeated without the polydioryanosiloxane, a stable emulsion was not obtained.
Example 4 Four parts Dy weiyht of a polydioryano-siloxane haviny the formula (cH3)3sioL(cH3) 2SiOlXL(Cfl3)(~)SiO]yL(Ctl3)(51)~zSi(CH3)3 wllerein x has a value of about 100, y has a value of about ;
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4S, ~ has a value of about ~.5, ~ denotes the dodecyl radical and ~ denotes the -C~c~2c~2(oc~2c~2)~(oc~c~c~c~3~OH
radical wherein p and ~ each have a value of about 24 was mixed with 1 part by weight (1.7 parts by volume) of an isoparaffin haviny a flash point of at least 10UF (Isopar~ M) to form a concentrate solution.
This concentrate, and ~ parts by weiyht of ethoxylated tridecylalcohol (Tergitol~ 15-S-3) were dissolved in 32 parts ~y welyht (39 parts by volume) of fuel oil ~2, usiny a paddle mlxer. The paddle mixer was rotated at 4U~ to 5U0 r.p.m. and 6~ parts by weiyht (4b. ~ parts ~y volume) of a 3~ percent by weiyht solution of CaCl~ in water was slowly added to the stirred solution. ~fter the brine had been completely adde~ the mixture was stirred for 30 minutes and a stable (at ieast ~ weeks) brine-in-fuel oil emulsion was obtained which had a particle size of less than 1 microlneter. This emulsion could `~e further diluted wit~l fuel oil ~2.
Exam~le 5 Example 4 was reyeated except that the ~rine was thickened with hydroxyethylcellulose before it was emulsified in the fuel-oil. An emulsion haviny a smaller particle size and a ~reater sta~ility than that of the emulsion of Example 4 was obtained.
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-~4-~xample 6 Four parts by weiyht of the polydioryanosiloxane use~ in Example 4 was mixed witn 1 part by weiyht (1.3 parts ~y volume) of Isopar~ M.
Tl~e resultiny concentrated solution, and 3 parts by wei~ht of dodecanol, were mixed with 33 parts by weiynt (~0.2 parts by volume) of diesel fuel using a three-bladed paddle mixer. The mixer was rotated at 4UU to 50u r.p.m. and 6~ parts by weight (26 parts by volume) of a ~rine containing ZnBr2 and CaBr~ was slowly added to the stirred solution. A thixotropic emulsion havin~ a brine particle size of less than U.5 micrometer and a stability of at least seven days at room temperature was o~tained. When this low-shear metilod was repeated in tne absence of dodecanol the resulting emulsion separated within 24 l~ours.
Exam~le 7 Example 6 was repeated except an identical alnount or decanol, instead of dodecanol, was used.
rhe resultlny emulsion was stable, but not ~uite as stable as the emulsion of Example 6.
Example 8 ~ xample 7 was repeated except that an identical weiyht of Alaska crude oil, instead of diesel fuel, was used. The resulting emulsion of neavy brine-in-li~uid hydrocar~on had an averaye particle si~e of less than 1 micrometer and was stable to separation for at least 7 days.
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~xample ~
About 4.5 parts ~y weight of the po'ydioryanosiloxane described in Example 4 was dissolved in 46.5 parts by weiyht (56.7 parts by volume) of diesel fuel #2. The resulting solution was placed in an Eppenbach mixer and agitated while 41.
parts ~y weiyht (1~.2 parts by volume~ of the heavy ~rine described in ~xample 6 (sold by ttle ~ow Chemical Compally~ as ~W-V) was slowly emulsified therein. The resultiny emulsion was thickened ~y addiny 7.2 parts ~y weiynt of an amille-treated bentonite clay (~entone~
~). The resultin~ composition of this invention ~ad an averaye particle size of less than 1 micrometer.
A portion of the thickened emulsion was placed in each of 5 stainless steel ayiny vessels, the vessels were pressurized with nitroyen and then sealed. One vessel was heated at 3~F for 5 days, after which tlle averaye particle size was no more than 2 micrometers. Another vessel was heated at 400E` for 7 days with similar results. Another vessel was heated at 500F for 5 days witn substantially identical results. Anotner vessel was heated at 600F
for ~ days with similar results. The remainin~ vessel was l~eated at 700~ for 5 days, after which some deyraded naterial was noted but the averaye particle size did not exceed ~ micrometers. T~lis example illustrates the thermal stability of a drilliny fluid composition of tnis invention.
.
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--;~b--Example 10 Four parts by weiyht of the polydiorganosiloxane described in Example 4 was dissolved in 31 parts by weiyht (37.~ parts by vol~ne) o~ diesel fuel #2. ~rhe resultiny solution was placed in an ~ppen~ac~l mixer and ayitated whiie bO parts by weiyht (26 parts by volume) of the heavy brine descrived in Example 6 and S parts ~y weiynt of t~le bentonite clay descri~ed in Example 9 were slowly added, se~uentially, thereto. Tne resultiny emulsion had an average brine particle size of no more than 1 micrometer. The thermal sta~ility of t~le emulsion at 5~0F for 5 days was evaluated as described in Example Y. The averaye particle size of the neated emulsion did not exceed ~ micrometers, with a few particles beiny as large as 5 micrometers.
Example 11 The polydioryanosiloxane described in ~xample ,- 1.6 ~arts by weight, was dissolved in 78 parts by weiyht (95.i parts by volume) of diesel fuel ~. The resultiny solution was placed in an Eppenbacn mixer and stirred while 14 parts by weiyht (10.8 parts by volume) of a liyht CaCl~ brine was slowly added thereto. The resulting emulsion was further thickened witn 6 parts ~y weight of an amine-treated bentonite clay (~entone~ 3~). The resultiny emulslon had an averaye brine particle si~e of frorl 0.3 to ~.5 micrometer.
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Claims (10)
1. An emulsion composition to be used in well-drilling and comprising (A) 1 to 75 parts by volume of a brine as a discontinuous phase, (B) 25 to 99 parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F as a continuous phase, and characterized by (C) 0.05 to 15 parts by weight, for every 100 parts by weight of brine plus liquid hydrocarbon, of a polydiorganosiloxane having the formula Z3SiO[(CH3)2SiO]x[(CH3)(R)SiO]y[(CH3)(Q)SiO]zSiZ3 wherein Q denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p(OCH2CHCH3)qOR", R denotes a monovalent hydrocarbon radical having from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive, or a Q radical, or an R radical, x has an average value of from 0 to 400, y has an average value of from 0 to 400, z has an average value of from 0 to 5, x + y + z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p + q has an average value sufficient to provide a formula weight of from 600 to 3500 for the -(OCH2CH2)p(OCH2CHCH3)q- portion of the Q
radical, there being an average of at least one Q radical and an average of at least one R radical per molecule of the polydiorgano-siloxane.
radical, there being an average of at least one Q radical and an average of at least one R radical per molecule of the polydiorgano-siloxane.
2. An emulsion composition according to claim 1 wherein the polydiorganosiloxane has the formula (CH3)3SiO[(CH3)(R)SiO]y[(CH3)(Q)SiO]zSi(CH3)3 wherein y and z are greater than zero and the sum of y + z has an average value of from 30 to 70.
3. An emulsion composition according to claim 2 wherein Q denotes a polyoxyalkylene radical having the formula -CH2CH2CH2(OCH2CH2)p(OCH2CHCH3)qOH, the sum of p + q has an average value of about 50, p has an average value of from about 25 to 50, q has an average value of from about 0 to 25 and X denotes an alkyl radical.
4. An emulsion composition according to claim 1 wherein the polydioryanosiloxane has the formula (CH3)3SiO[(CH3)2SiO]x[(CH3)(R)SiO]y[(CH3)(Q)SiO]zSi(CH3)3 wherein x has an average value of about 100, y has an avergge value of from about 30 to 70 and z has an average value of from 1 to 5.
5. An emulsion composition according to claim 4 wherein Q denotes a polyoxyalkylene radical having the formula -CH2CH2CH2(OCH2CH2)p(OCH2CHCH3)qOH, the sum of p + q has an average value of about 50, p has an average value of from about 25 to 50, q has an average value of from about 0 to 25 and R denotes an alkyl radical.
6. A method which is characterized by (I) mixing to form a solution, (i) 0.5 to 15 parts by weight of a polydioryanosiloxane having the formula Z3SiO[(CH3)2SiO]x[(CH3(R)SiO]y[(CH3)(Q)SiO]zSiZ3 wherein Q denotes a polyoxyalkylene radical having the formula -R'(OCH2CH2)p(OCH2CHCH3)qOR", R denotes a monovalent hydrocarbon radical having an average of from 6 to 18 carbon atoms, inclusive, R' denotes a divalent radical bonded to a silicon atom by a silicon-carbon bond, R" denotes a monovalent radical selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aryl, arylalkyl and acyl radicals, Z denotes a monovalent hydrocarbon radical having from 1 to 5 carbon atoms, inclusive, or a Q radical, or an R
radical, x has an average value of from 0 to 400, y has an average value of from 0 to 400, z has an average value of from 0 to 5, x + y + z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p + q has an average value sufficient to provide a formula weight of from 600 to 3500 for the -(OCH2CH2)p(OCH2CHCH3)q-portion of the Q radical, there being an average of at least one Q radical and an average of at least one R radical per molecule of the polydioryanosiloxane, and ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F, (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter, and (IV) mixing the emulsion of step (III) with cV parts by volume of the liquid hydrocarbon, wherein, V has a value of from 55 to 99 parts by volume, V' has a value of from 1 to 75 parts by volume, V + V' has a weight of 100 parts by weight, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, and a + b + c has a value of 1.
radical, x has an average value of from 0 to 400, y has an average value of from 0 to 400, z has an average value of from 0 to 5, x + y + z has an average value of from 30 to 400, p has an average value equal to or greater than the average value of q and p + q has an average value sufficient to provide a formula weight of from 600 to 3500 for the -(OCH2CH2)p(OCH2CHCH3)q-portion of the Q radical, there being an average of at least one Q radical and an average of at least one R radical per molecule of the polydioryanosiloxane, and ii) aV parts by volume of a liquid hydrocarbon selected from the group consisting of kerosene, diesel oil, crude oil, turbine fuel, mineral oil, gas oil and paraffins having a flash point of at least 100°F, (II) mixing the solution of step (I) with bV parts by volume of the liquid hydrocarbon, (III) mixing V' parts by volume of a brine with the solution of step (II) with sufficient shear energy to provide an emulsion having a brine particle size of less than 10 micrometers in diameter, and (IV) mixing the emulsion of step (III) with cV parts by volume of the liquid hydrocarbon, wherein, V has a value of from 55 to 99 parts by volume, V' has a value of from 1 to 75 parts by volume, V + V' has a weight of 100 parts by weight, a has a value of from greater than zero to 1, b has a value of from zero to less than 1, c has a value of from zero to less than 1, and a + b + c has a value of 1.
7. A method according to claim 6 wherein V
has a value of from 10 to 60 parts by volume and V' as a value of from 40 to 90 parts by volume.
has a value of from 10 to 60 parts by volume and V' as a value of from 40 to 90 parts by volume.
8. A method according to claims 6 wherein a has a value of less than 1.
9. A method according to claim 8 wherein b has a value of (1-a) and c has a value of zero.
10. A method according to claim 8 wherein a has a value of from 0.0001 to 0.1 to provide a concentrated solution of the polydioryanosiloxane which is shipped and/or stored before use.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/236,968 US4381241A (en) | 1981-02-23 | 1981-02-23 | Invert emulsions for well-drilling comprising a polydiorganosiloxane and method therefor |
| US236,968 | 1981-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1177634A true CA1177634A (en) | 1984-11-13 |
Family
ID=22891775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000392106A Expired CA1177634A (en) | 1981-02-23 | 1981-12-11 | Invert emulsions for well-drilling comprising a polydiorganosiloxane and method therefor |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4381241A (en) |
| EP (1) | EP0059037B1 (en) |
| JP (1) | JPS58500066A (en) |
| CA (1) | CA1177634A (en) |
| DE (1) | DE3263588D1 (en) |
| MX (1) | MX160613A (en) |
| WO (1) | WO1982002898A1 (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX156325A (en) * | 1981-05-20 | 1988-08-10 | Mexicano Inst Petrol | AN IMPROVED REVERSE EMULSION OF BALANCED ACTIVITY TO INHIBIT THE HYDRATION OF DELEZNABLE PASSES IN OIL WELLS |
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| US11180690B2 (en) | 2013-03-14 | 2021-11-23 | Flotek Chemistry, Llc | Diluted microemulsions with low surface tensions |
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| US2689219A (en) * | 1952-02-11 | 1954-09-14 | Stanolind Oil & Gas Co | Emulsion drilling fluid |
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| US2793996A (en) * | 1955-12-08 | 1957-05-28 | Pan American Petroleum Corp | Oil base drilling fluid |
| US2805722A (en) * | 1956-02-24 | 1957-09-10 | Exxon Research Engineering Co | Perforation wells |
| US2846458A (en) * | 1956-05-23 | 1958-08-05 | Dow Corning | Organosiloxane ethers |
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| US3709819A (en) * | 1971-05-14 | 1973-01-09 | Milchem Inc | Oil phase drilling fluid additive, composition and process |
| US3799874A (en) * | 1973-03-16 | 1974-03-26 | Atlantic Richfield Co | Well cementing |
| US4122029A (en) * | 1977-07-27 | 1978-10-24 | Dow Corning Corporation | Emulsion compositions comprising a siloxane-oxyalkylene copolymer and an organic surfactant |
| US4160776A (en) * | 1978-06-29 | 1979-07-10 | Olin Corporation | Alkoxy-bis (trialkoxysiloxy)-silane surfactants |
-
1981
- 1981-02-23 US US06/236,968 patent/US4381241A/en not_active Expired - Lifetime
- 1981-12-10 WO PCT/US1981/001638 patent/WO1982002898A1/en unknown
- 1981-12-10 JP JP82500450A patent/JPS58500066A/en active Pending
- 1981-12-11 CA CA000392106A patent/CA1177634A/en not_active Expired
-
1982
- 1982-02-05 EP EP82300588A patent/EP0059037B1/en not_active Expired
- 1982-02-05 DE DE8282300588T patent/DE3263588D1/en not_active Expired
- 1982-02-08 MX MX191293A patent/MX160613A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3263588D1 (en) | 1985-06-27 |
| WO1982002898A1 (en) | 1982-09-02 |
| JPS58500066A (en) | 1983-01-13 |
| EP0059037B1 (en) | 1985-05-22 |
| US4381241A (en) | 1983-04-26 |
| EP0059037A1 (en) | 1982-09-01 |
| MX160613A (en) | 1990-03-28 |
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