CA2057024A1 - Agent for increasing viscosity in non-aqueous fluid phases, process of making it and its use - Google Patents
Agent for increasing viscosity in non-aqueous fluid phases, process of making it and its useInfo
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- CA2057024A1 CA2057024A1 CA002057024A CA2057024A CA2057024A1 CA 2057024 A1 CA2057024 A1 CA 2057024A1 CA 002057024 A CA002057024 A CA 002057024A CA 2057024 A CA2057024 A CA 2057024A CA 2057024 A1 CA2057024 A1 CA 2057024A1
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- Prior art keywords
- agents
- compounds
- general formula
- drilling fluids
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
Abstract
The description relates to agents which affect rheology, especially for the controlled viscosity increase in non-aqueous fluid phases based on hydrophobic oil-dispersable mixed hydroxide coumpounds with an inorganic basic structure, in which said agents are formed at least partly from inorganic stratified compounds with a positive stratum charge based on 2-dimensional inorganic polycations (polycationic stratified compounds) and mono and/or polybasic acid anions with a marked oleophilic character. In addition, the invention concerns methods for the production of such agents. In a further embodiment, the use of these agents in non-aqueous fluid phases, especially as viscosity-increasing gel formers in W/O
invert drilling fluids with a closed oil phase, and the composition of such drilling fluids is described.
invert drilling fluids with a closed oil phase, and the composition of such drilling fluids is described.
Description
2 ~ -~3 ~ n ''~
Henkel ~GaA
Dr. FU/ku 07.12.19 P a t e n t A p p 1 i c a t i o n ~'Agents for increasing viscosity in non-aqueous liquid phases, processes for their production and their use"
_________________________________________________ _____________________ The invention relates to new possibilities for influencing and controlling the rheology of non-aqueous liquid phases and enables in particular a controlled increase in viscosity in liquids of this type.
The predeterminable regulation of the rheological behavior of non-aqueous liquid phases is of considerable iTFortance in ~any fields of technology. An important example is in the currently widely used non-aqueous drilling fluids based on so-called invert drilling fluids, which contain a dispersed aqueous phase in a continuous oil phase. An Important area of application for such drilling fluid systems is in off-shore wells for the development of petroleum and/or natural gas deposits. Tbday, however, such W/O-emulsions are put to quite general use as drilling-mud systems in land-based drilling, for example, in geothermal wells, water bore-holes, in the drilling of geoscientific bores and in drilling for the mi~ing industry.
In an important embodiment, the invent:ion relates to improved drilling fluids of this type of W/O-invext system, and therefore reference is made below to this area of application in particular, although the invention is in no way limited thereto.
In current practice, hydrophobized layered silicates of the bentonite group are used a~ the rheology-regulating additives for non-aqueous drilling fluids. Such products are ccmmercially available, for exa~ple, under the collective name ~Bentones". The surface hydrophobization necessary for incorporation into~the slightly polar to non-polar carrier fluid i8 usually carried out with quaternary ammonium ~altQ, the organic cations of which combine by m0an_ of electro~tatic interactions with the negatively charged layered-silicate pl~telets.
Such product are indeed industrially satisfactory, hut from ecological point of view they mus~ be regarded a~ problematic: the quaternary ammonium salts used for the hydLophobization generally exh~bit biocidal effects, and as a result the po~sibility of envlronmental damage cannot be ruled out.
...
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The invention begins with the problem of preparing substitutes which are ecologically less harmful, but are at least of the same value in industrial practice, for influencing and controlling the rheology of such non-aqueous li~lid phases. The technical solution of this problem begins with the knowledge that selected inorganic la~ered materials with a positive layer charge (inorganic polycations), which have been brought tO interaction with mono- and/or polybasic acid anions of marked oleophilic character, produce results, when used as rheology-regulating additives, at least of the same value as the hydrophobized bentonite oompounds used previously.
The subject of the invention is accordingly constituted in a first embodin:nt by agents for influencing the rheology, in particular for a controlled increase in the viscosity, of non-aqueous liquid phases based on hy~drophobic oil-dispersible mixed hydro~ide oompounds with an inorganic basic structure, such that the characterizing part for the invention is that these agents are formed at least partly by finely dispersed particles of inorganic layer compounds with a positive layer charge based on two-dimensional inorganic polycations (polycationic layer compounds) and monobasic and/or polybasic acid anions of marked oleophilic character.
Two-dimensional inorganic polycations with inner-crystalline charge equalization via mobile interstitial anions are also known as "double-layer hydroxides" and are described in many places in the literature.
See, for example, R. Allmann, "Doppelschichtstrukturen mit brucitahnlichen Schichtionen ...", Chimia 24, 99 to 108 (1970).
Chemically these compounds are mLxed hydroxD salts of di- to trivalent metal ions and can be characterized by the general formula M(II)1_~M(III~X(CH)2A~ n H20 in which M (II) represents at least one divalent metal ion, M (III) represents at least one trivalent metal ion and A represents an equivalent of a mono- and/or polybasic acid ~d x sig~ifies a number from 0.01 to 0.5 and n signifies a number o~ 0 to 20.
S~me of the properties of this cla~s of oompound~, e.g., their us~ ~s a catalyst material, as an ion exchanger and for some medical applications were summarized ~y W.T. Reichle ~Anionic Clay Minerals", CHE~IECH, J~n. 1986, p. 58 to 63). Variou~ pDssibilities for the industrial prcduction of the8e cc~p~unds are given in DE-OS 20 61 156.
A well characterized repre~n~ative of thi8 gr~up of sub8tance8 i8 the ~ . .
:
Henkel ~GaA
Dr. FU/ku 07.12.19 P a t e n t A p p 1 i c a t i o n ~'Agents for increasing viscosity in non-aqueous liquid phases, processes for their production and their use"
_________________________________________________ _____________________ The invention relates to new possibilities for influencing and controlling the rheology of non-aqueous liquid phases and enables in particular a controlled increase in viscosity in liquids of this type.
The predeterminable regulation of the rheological behavior of non-aqueous liquid phases is of considerable iTFortance in ~any fields of technology. An important example is in the currently widely used non-aqueous drilling fluids based on so-called invert drilling fluids, which contain a dispersed aqueous phase in a continuous oil phase. An Important area of application for such drilling fluid systems is in off-shore wells for the development of petroleum and/or natural gas deposits. Tbday, however, such W/O-emulsions are put to quite general use as drilling-mud systems in land-based drilling, for example, in geothermal wells, water bore-holes, in the drilling of geoscientific bores and in drilling for the mi~ing industry.
In an important embodiment, the invent:ion relates to improved drilling fluids of this type of W/O-invext system, and therefore reference is made below to this area of application in particular, although the invention is in no way limited thereto.
In current practice, hydrophobized layered silicates of the bentonite group are used a~ the rheology-regulating additives for non-aqueous drilling fluids. Such products are ccmmercially available, for exa~ple, under the collective name ~Bentones". The surface hydrophobization necessary for incorporation into~the slightly polar to non-polar carrier fluid i8 usually carried out with quaternary ammonium ~altQ, the organic cations of which combine by m0an_ of electro~tatic interactions with the negatively charged layered-silicate pl~telets.
Such product are indeed industrially satisfactory, hut from ecological point of view they mus~ be regarded a~ problematic: the quaternary ammonium salts used for the hydLophobization generally exh~bit biocidal effects, and as a result the po~sibility of envlronmental damage cannot be ruled out.
...
i:
;': ' - 2 ~ 7~
The invention begins with the problem of preparing substitutes which are ecologically less harmful, but are at least of the same value in industrial practice, for influencing and controlling the rheology of such non-aqueous li~lid phases. The technical solution of this problem begins with the knowledge that selected inorganic la~ered materials with a positive layer charge (inorganic polycations), which have been brought tO interaction with mono- and/or polybasic acid anions of marked oleophilic character, produce results, when used as rheology-regulating additives, at least of the same value as the hydrophobized bentonite oompounds used previously.
The subject of the invention is accordingly constituted in a first embodin:nt by agents for influencing the rheology, in particular for a controlled increase in the viscosity, of non-aqueous liquid phases based on hy~drophobic oil-dispersible mixed hydro~ide oompounds with an inorganic basic structure, such that the characterizing part for the invention is that these agents are formed at least partly by finely dispersed particles of inorganic layer compounds with a positive layer charge based on two-dimensional inorganic polycations (polycationic layer compounds) and monobasic and/or polybasic acid anions of marked oleophilic character.
Two-dimensional inorganic polycations with inner-crystalline charge equalization via mobile interstitial anions are also known as "double-layer hydroxides" and are described in many places in the literature.
See, for example, R. Allmann, "Doppelschichtstrukturen mit brucitahnlichen Schichtionen ...", Chimia 24, 99 to 108 (1970).
Chemically these compounds are mLxed hydroxD salts of di- to trivalent metal ions and can be characterized by the general formula M(II)1_~M(III~X(CH)2A~ n H20 in which M (II) represents at least one divalent metal ion, M (III) represents at least one trivalent metal ion and A represents an equivalent of a mono- and/or polybasic acid ~d x sig~ifies a number from 0.01 to 0.5 and n signifies a number o~ 0 to 20.
S~me of the properties of this cla~s of oompound~, e.g., their us~ ~s a catalyst material, as an ion exchanger and for some medical applications were summarized ~y W.T. Reichle ~Anionic Clay Minerals", CHE~IECH, J~n. 1986, p. 58 to 63). Variou~ pDssibilities for the industrial prcduction of the8e cc~p~unds are given in DE-OS 20 61 156.
A well characterized repre~n~ative of thi8 gr~up of sub8tance8 i8 the ~ . .
:
7 ~
naturally occurring, but also synthetically producible hydrotalcite, a magnesium-aluminium-hydroxocarbonate of the approximate ccmposition Mg6A12(OH)16CO3 . 4H20, the structure of which was determined by X-ray photography (R. Allmann and H.P. Jepsen, "Die Struktur des Hydrotalkits", N. Jahrb. Mineral. Monatsh. 1969, p. 544-5S1).
The modification of hydrotalcite-like layered compounds by treatment with anionic surface-active agents is also known. For example, DE-PS
19 632 mentions that hydrotalcite treated in this way is particularly suitable for the stabilization of halogen-containing synthetic materials. The use according to the invention of the reaction products of inorganic polycationic layered materials with acid anions of a marked oleophilic character for influencing and controlling the rheolcgy of non-aqueous liquid phases, in particular in the sense of a controlled increase in viscosity, is not, however, anticipated by this patent.
EP-OS 207 811 describes the use in aqueous drilling fluids of non-hydrophobized mixed metal hydroxides which are produced in a particularly finely particulate form by an expensive process. In contrast, the aim of the invention is to influence the rheology of particularly the non-aqueous liquid phases. The hydrophobization provided according to the invention of the polycationic layer compounds through the incorporation of mono- andtor polybasic acid anions of marked oleophilic character into the polycationic inorganic material is required for this.
The mixed hydroxo salts of divalent and trivalent metal ions provided according to the invention make , in the form m3dified according to the invention, hydrophQbic finely dispersed solids of the following general formula I
M(II)1_~M(III)X(OH)2A~ n H20 (I) in which M(II) represents at least one divalent metal ion M(III) represents at least one trivalent metal ion and A represent an equivalent of anions o~ mono- and/or poly~asic acids at least partly of a marked oleophilic character an~
x signifi~ a number from 0.01 to 0.5 and also n signifies a number frcm 0 to 20, such that at least such a part of the radical A i9 derived from oorresponding acids of marked oleophilic character that the ~olids of .~ .
.
;, 2 ~ i` q the general formula 1 are hydrophobic.
Hydrophobic behavior already appears on the incorporation of 2 to 3 %by weight (referred to the total quantity of solid) of an acid anion of marked oleophilic character.
A solid is understood to be hydrophobized in the sense of theinvention, when more than 90 % thereof disperses in the oil phase in the following test: 1 g of the test substance is placed in a 100-ml glass b~aker in 50 ml of totally deionized water. m e aqueous phase is provided with a layer of 5 ml of silioon oil (for example, the cammercial product ~Baysilon 100" of the ooTpar.y BAYER AG) and the tw~
phases are intermuxed by stirring with a magnetic stirrer. The hydrophobic part of the solid disperses in the oil phase, which when there is a high solids charge can clump together and sink to the bott~m.
The divalent metal ions M(II) frGm formula I are fon~ed in aparticularly preferred emtDdlment of the teaching according to the invention ~y magnesium, calcium, barium or zinc or any mixtures thereof. I~he invention is not, however, limited thereto. In principle, any divalentimetal ions cani~e used, as disclosed in a wider context, for example, in the already cited EP-OS 207 811.
In the context of the present invention, the preferred metal ionsM(III) ~rom the ocmpounds of steneral formula I are aluminium and/or iron. It is also true here that these trivalent metal ions can be used in the wider context as disclosed, for example, in the a'cove E~lropean Patent Application.
According to the invention the radical A fram the general fonmula I,which is formed at least partly by the hydrophobizing acid radicals, is particularly important. m ese are anions of oleophilic organic o3mpounds with at lea t one salt~forming acid s~roup. A suitable acid gxoup of this type is the carboxyl group. The invention i8 not, however, limited thereto. In addition to, or in pla oe of, such carboxylic acid radicals, radieals of hetero-organic acids are also suitable, and in particular heterc-organic acids based on sulphur and/or phosphoru3 can be considered. me following also applies here:
The acid grouping, with the respective nucleus of the acid grou~ can beattached ~;rectly ~o tha oleophiLic ba~ic structure. In particular in the ca6e of polybasic acid groups, the anion-forming acid radical can Ln any case also ~e linked by means of hetero atoms - for example, oxygen - to the oleophilic organic radical. ThiR latter embodimen:t iS
ignifiCant Ln particular for polybasic acids such a~ sulfonic acids or _ 5 2 ~ 3 phosphonic acids, which can then also be used in the fonm of their acidic esters of marked oleophilic character.
It is generally the case that, in preferred embodlments, the agentsaccording to the invention of the general formula I are compounds in which the hydrophobizing anionic acid radicals A derive from compounds R-X (IIa) and/or from oompounds of the formula R-C-Y (IIb); the following applies for these tWD general formula~:
R represents a markedly oleophilic hydrocarbon radical with preferablyat least 6 carbon atoms, X represents the anionic radicals of the acid grouping, which can preferably be derived from -COOH, -$O3H and/or -PO3HR~. Y in a possible embodiment is the anionic radical of -SO3H or -PO3HR~, and finally in these cases R can signify a hydrogen radical or a hydrocarbon radical - particularly an alkyl radical - with, for example, up to 20 carbon atoms.
Particularly suitable acid anions A from the general formula I derivefrom acids which fall under the general formulae IIa and/or IIb, in which the radical R represents a linear or branched, saturated or unsaturated alkyl and/or arylalkyl radical. Ihese pure hydrocarbon radicals can also be substituted. Suitable substituents are in particular hydroxyl, thiol andtor a~ino groups. It is particularly preferred ~or the radical R to represent hydrocarbons of the aforementioned type with 8 to 36 car~on atoms. In particular, oorresponding carboxylic acids of natural and/or synthetic origin can be suitable here, and carboxylic acid mLxtures of natural origin can be of particular significance. Without exception these are hydrophobizing anionic radicals A in the general formula I which derive frcm environmentally acoeptable ccmpounds of low toxicity and therefore are particularly suitable for this aspect of the objective of the invention.
In a further embodiment the invention includes processes for theproduction of the aforementioned agent and in particular of finely dispersed oampounds of the general formula I. In principle there are several possible methods:
In a first embodhnYnt, polycationic layer compounds of the above typeare initially produced in a manner known per se, in which hcwever the inner-crystalline charge equalization is effected by anions, which differ in thp;r constitution from the anionic radicals A from general formula I a defined acoording to the invention. ~oth inorganic and organic acid radicals can be oonsiderad here and in gener~l the salt-forming acid radicals fram the metal salts used for the synthesis of the double-layer hydroKides are present. In a subsequent reaction the 6 - 2~ n~ 1 mlxed hydroxide compounds initially formed, are treated with the selected ~ono- and/or polybasic acids of marked oleophilic character and/or their salts soluble in the reaction medium. At least a covering hydrophobization of the polycationic inorganic layered materials occurs on interchange of salt. Hydroxo salts of this type are then oil-dispersible and can be used for rheology control in the sense of the invention.
This subsequent hydrophobization of the previously formed cationiclayered cc~pounds is, however, only one possibility for the preparation of agents for the application according to the invention. More favorable alternatives consist in carrying out the production of the mlxed metal hydroxo salts directly in the presence of the hydrophobizing acids or acid anions.
In one emkcdiment of the invention, with the aid of liquid phases, e.g.the follc~ing method is used : An alkalized solution of the hydrophobizing acid, e.g. of an alkanic acid or an alkanic acid mixture, is mixed with a solution of the divalent and trivalent metal cations in the necessary molar ratio. As the liquid phase, or solvent, water and~or aqueous organic liquid phases can be used. The mixed hydroxo salt is then formed in this system in a manner known per se, by heating. Detailed specifications for the formation of double-layer hydroxides of the type referred to here can be found in the cited prior art.
A further and particularly suitable synthesis method consists in thereaction of the hydroxide or hydroxides of one metal cc~ponent(s) thus, for example, of the divalent mLtal cc~ponent - with an easily meltable salt of the other metal component(s) required in the melt, such that these latter named metal salts already contain the mono-andJor polybasic acid anions of a marked oleophilic character as salt-forming components. After the reactants have reacted in the nelt, the c~oled melt is then ground to pGwder.
In a furth~r embodiment the invention includes the use of the agentdescribed a~ove in non~aqueous liquid phases, particularly as a structure form~r and viscosity regulator. It is particularly important in the context of the invention to use this agent as a rheology-nndifying agent in W/O invert dr;lling fluids with a continuous oil phase and a dispersed aqueous phase.
Fin lly, W/O invert drilling fluids of the latter type fall within thescope of the inYention which are characteriæed in that they contain as a rheology-mDdifying agent a~ lea~t partly the æ orementioned agents of the invention, in particular tho~e of the general formula I. For 2 ~
the structure, the nature and the req~lireTent-profile of such invert drilling fluid systems, refer to the relevant prior art. Drilling fluids of this type consist of a 3-phase system: oil, water and finely particulate solids. For the stabilization of the aqueous phase which is finely dispersed in the continuous oil phase, and for the stabilization of the total system as well as for the adjustment of the desired application properties, a number of a~;tives are provided, particularly emulsifiers, weighting agents, fluid-loss additives, alkali reserves, viscosity regulators and the like. For details see, for example, the publication by P.A. Boyd et al. "New Base Oil Used in Low-Tbxicity Oil Muds" Journal of Petroleum Technology, 1985, 137 to 142 and R.B. Bennett "New Drilling Fluid Technology - Mineral Oil Mud"
Journal of Petroleum Technology, 1984, 975 to 981 and in the literature cited therein.
Selected diesel oil fractions are used as the oil phase, and inparticular increasingly in recent times pure hydrocar~on oils which are at least largely free from aromatics. The relevant technology has for some time recoc~nized the significance of the environmental problems triggerecl by these oil phases. This explains the increased significance of the oil-base muds based on so-called non-polluting oils. In adclition to the mineral oil fractions free frcm aromatics, oil phases based on esters in particular belong to the class of non-polluting oils. Ester oils, or invert drilling-mud systems based on ester oils, which are usable and distinctly improved particularly fm m the point of view of environmental protection, are the subject matter of a number of the Applicant's earlier Applications. See here in particular the Applications P 38 42 659.5 and P 38 42 703.6, the earlier Patent Applications P 39 07 391.2 and P 39 07 392.0 and th~
associated further development of such invert drilling fluids based on ester-oils in the Applicant~s earlier Application P 3~ 03 785.1. The disclosure of all these earlier Applications is in principle also valid for the modification described in the present invention, the subject m~tter of which is the replacement of the structure-formlng gel-forming agent. The disclosure of these named earlier Applications as to the basic nature of such W/O invert drilling fluids i9 hereby expressly included in the subject matter of the present invention disclosure.
Finally, the earlier A~plications P 39 11 238.1 and P 39 11 299.3should also be oonsidered in this context, which likewise refer to new systems on a WJC-base for application in drilling fluids and are characterized by improved environmental acceptability. m e structure-forming ~elling agents described aco~rding to the invention can be used to advantage in all these materials.
The quantity of visoosifier used acco~ding to the invention oorresponds - 8 - 2~ ;,/7 approxLmately to the quantities of the previously used oorponents based on cation-modified finely particulate bentonites. ~dditional quantities are therefore suitable in particular in the range of acout 0.5 to 5 % by weight, preferably in the range of about 0.8 to 3.5 % by weight, referred to the oil phase.
The following also applies:
Invert drilling muds of the type referred to here usually contain, together with the continuous oil phase, the finely dispersed aqueous phase in quantities from about 5 to 45 ~ by weight and preferably in quantities from about 10 to 25 ~ by weight. Particular significance can be attributed to the range from about 10 to 25 % by weight of dispersed aqueous phase.
The following rheologiQl data apply for the rheology of the invert drilling fluids preferred according to the invention: Plastic viscosity (PV) in the range from a~out 10 to 60 mPa.s, preferably from about 15 to 40 mPa.s, yield point YP) in the range from about 5 to 40 lb/100 ft2, preferably from about 10 to ~5 lb/100 ft2 _ each determined at 50C. For the determination of these parameters, for the measuring methods used therein and for the rest of the usual composition of the invert drilling fluids described here, the details apply as in the prior art, cited above and described in detail, for example, in the "Manual of Drilling Fluids Technoloqy" of the CQmpany ML Baroid, London, GB, and in particular under the chapter "Mud Testing - Tbols and Technique~" and "Oil Mud Technology" which is freely accessible to interested experts. In sumnary for the purposes of completion of the invention disclosure the follc~ing can be said:
The emulsifiers that can be used in practice are syst~ms suitable for the formation of the required ~/O-emulsions. In particular, selected oleophilic fatty acid salts, e.g. those based on amidoam m e compounds, can be considered.
Examples of these are described in US PS 4,374,737 and the literature cited therein. A particularly suitable type of emLlsifier is the product sold by the cc~pany NL Baroid under the brand name "EZ-mul".
Emulsifiers of this type are sold crmmercially as hic~hly-concentrated acti~e substan oe preparations and can, for e~ample, be used in amounts from about 2.5 to 5 % by weight, particularly in amounts from about 3 to 4 ~ ~y ~eic~ht - referred to the oil phase.
~ydrophobized lignite particularly is used in practice as the fluid-1068 additive and thus in particular to form a d~n6e ooating -of a : , .
., ., ~ ~ ~ 7 !~ q _ 9 _ largely liquid-impermeable film on the bore-hole ~alls. Suitable amounts lie in the range, for example, frQm about 15 to 20 Ib/bbl or from about 5 to 7 ~ by weight, referred to the oil phase.
Barite is the weighting agent generally used in relevant applications to establish the necessary pressure compensation, the amounts added being varied according to the drilling conditions to be anticipated in each case. By adding barite, it is, for example, possible to raise tne specific weight of the drilling fluid to 2.S and preferably to a value in the range of about 1.3 to 1.6.
The dispersed aqueous phase in these invert drilling fluids is loaded with soluble salts. Calcium chloride and/or potassium chloride are used predaminantly here, saturation of the aqueous phase at room temperature with the soluble salt being preferred.
The aforementioned emulsifiers, or emulsifier systems, optionally also serve to improve the oil wettability of the inorganic weighting materials. In addition to the amL~Damides already mentioned, further examples are alkylbenzene sulfonates and imidazoline conpounds.
Additional information regarding the relevant Prior ~rt can be found in the following publications: GB 2 158 437, EP 229 912 and DE 32 47 123.
:
7 ~
E x a m p 1 e s Example 1 200 g of coTmercial hydrotalcite is suspended in one liter of i-propanol. 132 g of lauric acid is dissolved as far as possible in one liter of i-propanol and added to the hydrotalcite suspension. The resulting suspension is stirred for four hours at -oom temperature and then refluxed for one hour. Afterwards the solids are îiltered off, washed with i-propanol and dried at 110C in the drying cabinet.
Example 2 200 g of cG~mercial hydrotalcite is suspended in one liter of i-propanol. 187 g of stearic acid is dissolved as far as possible in one liter of i-propanol and added to the hydrotalcite suspension. me resulting suspension is stirred for four hours at room temperature and then refluxed for one hour. Afterwards the solids are filtered off, washed with i-propanol and dried in the drying cabinet at 110C.
Example 3 315.5 g of an industrial colza-oil/split fatty acid mlxture is mLxed and stirred with 400 g of o~mmercial hydrotalcite. The semi-solid, crumbly product is after-dried in the drying cabinet at 110C.
Example 4 1S5.6 g of an industrial colza-oil/split fatty acid mLxture i6 mixed and stirred with 400 g of oom~ercial hydrotalcite. The semi-solid, crumbly product is after-dried in the drying cabinet at 110C.
EKamPle 5 A mLXture of 22.5 g of Al(OH)3 and 100 g of zinc stearat~ is melted at125 to 130C and held for an hour at this temperature. ~he oooled solidified melted material is then ground to powder.
Example 6 100 g of ocmmercial hydrotalcite is suspended in one liter of water ~nd 67.2 g of dodecyIbenzenesulfonic acid i8 add~d. The suspension i~
stirred for one hour at room temperature, the solid matter i8 drawn off, washed with water and dried.
Example 7 1800 ml of water i9 mlxed with 200 g of an industrial colza-oilJsplit fatty acid mixture and with 500 g of a 50 ~ by weight sodium hydroxide solution. A solution of 230 g of magnesium nitrate/hexahydrate and 169 g of aluminium-nitrate-nonahydrate in 630 g of water is allowed to drop into this muxture under stirring at room temperature (fcam formationl).
After the addition is complete, stirring is continued for four hours at 65C, the solid matter was drawn off, washed with water and dried at 110C in the drying cabinet.
Ex1mple 8 A solution is prepared of 410 g of magnesium nitrate/hexahydrate and300 g of aluminium nitrate/nonahydrate in 8000 g of totally deionized water and a second solution is prepare from 448 g of 50 ~ sodium hydroxide solution and 160 g of scdium car~onate (water free) in 8000 g of totally deionized water. The two solutions are pumped with peristaltic (hose) pumps through the leg of a Y-shaped tube into a receiver, the hydrotalcite precipitate fonmed is dra~n off and washed with totally deionized water. m e pasty product with a solids content of a maximu~ of 70 ~ (determlned by drying at 110C) is not dried further so that the fine primary particles do not aggl~merate further.
100 g of the acove paste with a solids content of about 25 % by weight is suspended in 250 ml of fully deionized water and mlxed at room temperature with 2.5 g of phosphonoacetic acid monoethylester. The mlxture is stirred, filtered, washed ~ith water and dried at 110 in the drying cabinet.
Example 9 100 g of the hydrotalcite paste from Example 8 is suspended in 250 ml of fully dei~niæed water and muxed at room temperature with 5 g of 12-hydroxystearic acid. The mixture is stirred for one hour at room temperature, filtered, washed with water and dried at 110C in the drying cabinet.
Example 10 Rheology-regulating additive~ according to the invention and state-of-the-art comparati~e produ~ts were tested in a diesel drilling fluid with the follcwing formulation:
168 g diesel oil 6 g W/0-emLlsifier ~"Invermul~ of the oompany NL Baroid) - 12 - `` ' "`' `~
3 g lime 6 g organophilic lignite ("Duratone" of the ooTpany NL Bar~id) 3 g W/0-emulsifier ("EZ-mul NT" of the coTpany NL Baroid) 73 g CaC12-solution 470 g barite ____________________ 2 g rheology-regulating additive according to the table below As the test parameters, the following were measured: Plastic viscosity(PV) in cP and yield point (YP) in lb/100 ft2 and the gel streng~h (GS) in lb/100 ft2 for 10 sec. and 10 mun., in which in each case the first figure in the table refers to the value after the production of the fluid, the seoond figure refers to the value after ageing (16 hours) at 250F.
Additive from Example No. PV YP GS
___________.________________________________________________________ 1 41 / 3510 ~ 7 4;5 ~ 4;6 2 43 / 361~ / 13 5;6 / 5j6 4 42 / 4114 / 11 5;6 ~ 5;6 43 / 4310 / 11 4;5 / 5;6 6 42 / 42~ / 11 4;5 / 5;7 7 43 / 4311 / 8 5;6 / 5;6 8 40 / 351~ / 11 4;4 / 4;5 9 41 / 411~ / 14 4;4 ~ 5;6 Geltone II
(oomparison) 50 / 453'3 J 39 15;18 / 15;19 Cmnigel (oomparison) 47 / 4419 / 41 8;11 / 16;21 Perchem (comparison) 50 / 4521 / 42 8;10 / 16;20 .
, .~ .
naturally occurring, but also synthetically producible hydrotalcite, a magnesium-aluminium-hydroxocarbonate of the approximate ccmposition Mg6A12(OH)16CO3 . 4H20, the structure of which was determined by X-ray photography (R. Allmann and H.P. Jepsen, "Die Struktur des Hydrotalkits", N. Jahrb. Mineral. Monatsh. 1969, p. 544-5S1).
The modification of hydrotalcite-like layered compounds by treatment with anionic surface-active agents is also known. For example, DE-PS
19 632 mentions that hydrotalcite treated in this way is particularly suitable for the stabilization of halogen-containing synthetic materials. The use according to the invention of the reaction products of inorganic polycationic layered materials with acid anions of a marked oleophilic character for influencing and controlling the rheolcgy of non-aqueous liquid phases, in particular in the sense of a controlled increase in viscosity, is not, however, anticipated by this patent.
EP-OS 207 811 describes the use in aqueous drilling fluids of non-hydrophobized mixed metal hydroxides which are produced in a particularly finely particulate form by an expensive process. In contrast, the aim of the invention is to influence the rheology of particularly the non-aqueous liquid phases. The hydrophobization provided according to the invention of the polycationic layer compounds through the incorporation of mono- andtor polybasic acid anions of marked oleophilic character into the polycationic inorganic material is required for this.
The mixed hydroxo salts of divalent and trivalent metal ions provided according to the invention make , in the form m3dified according to the invention, hydrophQbic finely dispersed solids of the following general formula I
M(II)1_~M(III)X(OH)2A~ n H20 (I) in which M(II) represents at least one divalent metal ion M(III) represents at least one trivalent metal ion and A represent an equivalent of anions o~ mono- and/or poly~asic acids at least partly of a marked oleophilic character an~
x signifi~ a number from 0.01 to 0.5 and also n signifies a number frcm 0 to 20, such that at least such a part of the radical A i9 derived from oorresponding acids of marked oleophilic character that the ~olids of .~ .
.
;, 2 ~ i` q the general formula 1 are hydrophobic.
Hydrophobic behavior already appears on the incorporation of 2 to 3 %by weight (referred to the total quantity of solid) of an acid anion of marked oleophilic character.
A solid is understood to be hydrophobized in the sense of theinvention, when more than 90 % thereof disperses in the oil phase in the following test: 1 g of the test substance is placed in a 100-ml glass b~aker in 50 ml of totally deionized water. m e aqueous phase is provided with a layer of 5 ml of silioon oil (for example, the cammercial product ~Baysilon 100" of the ooTpar.y BAYER AG) and the tw~
phases are intermuxed by stirring with a magnetic stirrer. The hydrophobic part of the solid disperses in the oil phase, which when there is a high solids charge can clump together and sink to the bott~m.
The divalent metal ions M(II) frGm formula I are fon~ed in aparticularly preferred emtDdlment of the teaching according to the invention ~y magnesium, calcium, barium or zinc or any mixtures thereof. I~he invention is not, however, limited thereto. In principle, any divalentimetal ions cani~e used, as disclosed in a wider context, for example, in the already cited EP-OS 207 811.
In the context of the present invention, the preferred metal ionsM(III) ~rom the ocmpounds of steneral formula I are aluminium and/or iron. It is also true here that these trivalent metal ions can be used in the wider context as disclosed, for example, in the a'cove E~lropean Patent Application.
According to the invention the radical A fram the general fonmula I,which is formed at least partly by the hydrophobizing acid radicals, is particularly important. m ese are anions of oleophilic organic o3mpounds with at lea t one salt~forming acid s~roup. A suitable acid gxoup of this type is the carboxyl group. The invention i8 not, however, limited thereto. In addition to, or in pla oe of, such carboxylic acid radicals, radieals of hetero-organic acids are also suitable, and in particular heterc-organic acids based on sulphur and/or phosphoru3 can be considered. me following also applies here:
The acid grouping, with the respective nucleus of the acid grou~ can beattached ~;rectly ~o tha oleophiLic ba~ic structure. In particular in the ca6e of polybasic acid groups, the anion-forming acid radical can Ln any case also ~e linked by means of hetero atoms - for example, oxygen - to the oleophilic organic radical. ThiR latter embodimen:t iS
ignifiCant Ln particular for polybasic acids such a~ sulfonic acids or _ 5 2 ~ 3 phosphonic acids, which can then also be used in the fonm of their acidic esters of marked oleophilic character.
It is generally the case that, in preferred embodlments, the agentsaccording to the invention of the general formula I are compounds in which the hydrophobizing anionic acid radicals A derive from compounds R-X (IIa) and/or from oompounds of the formula R-C-Y (IIb); the following applies for these tWD general formula~:
R represents a markedly oleophilic hydrocarbon radical with preferablyat least 6 carbon atoms, X represents the anionic radicals of the acid grouping, which can preferably be derived from -COOH, -$O3H and/or -PO3HR~. Y in a possible embodiment is the anionic radical of -SO3H or -PO3HR~, and finally in these cases R can signify a hydrogen radical or a hydrocarbon radical - particularly an alkyl radical - with, for example, up to 20 carbon atoms.
Particularly suitable acid anions A from the general formula I derivefrom acids which fall under the general formulae IIa and/or IIb, in which the radical R represents a linear or branched, saturated or unsaturated alkyl and/or arylalkyl radical. Ihese pure hydrocarbon radicals can also be substituted. Suitable substituents are in particular hydroxyl, thiol andtor a~ino groups. It is particularly preferred ~or the radical R to represent hydrocarbons of the aforementioned type with 8 to 36 car~on atoms. In particular, oorresponding carboxylic acids of natural and/or synthetic origin can be suitable here, and carboxylic acid mLxtures of natural origin can be of particular significance. Without exception these are hydrophobizing anionic radicals A in the general formula I which derive frcm environmentally acoeptable ccmpounds of low toxicity and therefore are particularly suitable for this aspect of the objective of the invention.
In a further embodiment the invention includes processes for theproduction of the aforementioned agent and in particular of finely dispersed oampounds of the general formula I. In principle there are several possible methods:
In a first embodhnYnt, polycationic layer compounds of the above typeare initially produced in a manner known per se, in which hcwever the inner-crystalline charge equalization is effected by anions, which differ in thp;r constitution from the anionic radicals A from general formula I a defined acoording to the invention. ~oth inorganic and organic acid radicals can be oonsiderad here and in gener~l the salt-forming acid radicals fram the metal salts used for the synthesis of the double-layer hydroKides are present. In a subsequent reaction the 6 - 2~ n~ 1 mlxed hydroxide compounds initially formed, are treated with the selected ~ono- and/or polybasic acids of marked oleophilic character and/or their salts soluble in the reaction medium. At least a covering hydrophobization of the polycationic inorganic layered materials occurs on interchange of salt. Hydroxo salts of this type are then oil-dispersible and can be used for rheology control in the sense of the invention.
This subsequent hydrophobization of the previously formed cationiclayered cc~pounds is, however, only one possibility for the preparation of agents for the application according to the invention. More favorable alternatives consist in carrying out the production of the mlxed metal hydroxo salts directly in the presence of the hydrophobizing acids or acid anions.
In one emkcdiment of the invention, with the aid of liquid phases, e.g.the follc~ing method is used : An alkalized solution of the hydrophobizing acid, e.g. of an alkanic acid or an alkanic acid mixture, is mixed with a solution of the divalent and trivalent metal cations in the necessary molar ratio. As the liquid phase, or solvent, water and~or aqueous organic liquid phases can be used. The mixed hydroxo salt is then formed in this system in a manner known per se, by heating. Detailed specifications for the formation of double-layer hydroxides of the type referred to here can be found in the cited prior art.
A further and particularly suitable synthesis method consists in thereaction of the hydroxide or hydroxides of one metal cc~ponent(s) thus, for example, of the divalent mLtal cc~ponent - with an easily meltable salt of the other metal component(s) required in the melt, such that these latter named metal salts already contain the mono-andJor polybasic acid anions of a marked oleophilic character as salt-forming components. After the reactants have reacted in the nelt, the c~oled melt is then ground to pGwder.
In a furth~r embodiment the invention includes the use of the agentdescribed a~ove in non~aqueous liquid phases, particularly as a structure form~r and viscosity regulator. It is particularly important in the context of the invention to use this agent as a rheology-nndifying agent in W/O invert dr;lling fluids with a continuous oil phase and a dispersed aqueous phase.
Fin lly, W/O invert drilling fluids of the latter type fall within thescope of the inYention which are characteriæed in that they contain as a rheology-mDdifying agent a~ lea~t partly the æ orementioned agents of the invention, in particular tho~e of the general formula I. For 2 ~
the structure, the nature and the req~lireTent-profile of such invert drilling fluid systems, refer to the relevant prior art. Drilling fluids of this type consist of a 3-phase system: oil, water and finely particulate solids. For the stabilization of the aqueous phase which is finely dispersed in the continuous oil phase, and for the stabilization of the total system as well as for the adjustment of the desired application properties, a number of a~;tives are provided, particularly emulsifiers, weighting agents, fluid-loss additives, alkali reserves, viscosity regulators and the like. For details see, for example, the publication by P.A. Boyd et al. "New Base Oil Used in Low-Tbxicity Oil Muds" Journal of Petroleum Technology, 1985, 137 to 142 and R.B. Bennett "New Drilling Fluid Technology - Mineral Oil Mud"
Journal of Petroleum Technology, 1984, 975 to 981 and in the literature cited therein.
Selected diesel oil fractions are used as the oil phase, and inparticular increasingly in recent times pure hydrocar~on oils which are at least largely free from aromatics. The relevant technology has for some time recoc~nized the significance of the environmental problems triggerecl by these oil phases. This explains the increased significance of the oil-base muds based on so-called non-polluting oils. In adclition to the mineral oil fractions free frcm aromatics, oil phases based on esters in particular belong to the class of non-polluting oils. Ester oils, or invert drilling-mud systems based on ester oils, which are usable and distinctly improved particularly fm m the point of view of environmental protection, are the subject matter of a number of the Applicant's earlier Applications. See here in particular the Applications P 38 42 659.5 and P 38 42 703.6, the earlier Patent Applications P 39 07 391.2 and P 39 07 392.0 and th~
associated further development of such invert drilling fluids based on ester-oils in the Applicant~s earlier Application P 3~ 03 785.1. The disclosure of all these earlier Applications is in principle also valid for the modification described in the present invention, the subject m~tter of which is the replacement of the structure-formlng gel-forming agent. The disclosure of these named earlier Applications as to the basic nature of such W/O invert drilling fluids i9 hereby expressly included in the subject matter of the present invention disclosure.
Finally, the earlier A~plications P 39 11 238.1 and P 39 11 299.3should also be oonsidered in this context, which likewise refer to new systems on a WJC-base for application in drilling fluids and are characterized by improved environmental acceptability. m e structure-forming ~elling agents described aco~rding to the invention can be used to advantage in all these materials.
The quantity of visoosifier used acco~ding to the invention oorresponds - 8 - 2~ ;,/7 approxLmately to the quantities of the previously used oorponents based on cation-modified finely particulate bentonites. ~dditional quantities are therefore suitable in particular in the range of acout 0.5 to 5 % by weight, preferably in the range of about 0.8 to 3.5 % by weight, referred to the oil phase.
The following also applies:
Invert drilling muds of the type referred to here usually contain, together with the continuous oil phase, the finely dispersed aqueous phase in quantities from about 5 to 45 ~ by weight and preferably in quantities from about 10 to 25 ~ by weight. Particular significance can be attributed to the range from about 10 to 25 % by weight of dispersed aqueous phase.
The following rheologiQl data apply for the rheology of the invert drilling fluids preferred according to the invention: Plastic viscosity (PV) in the range from a~out 10 to 60 mPa.s, preferably from about 15 to 40 mPa.s, yield point YP) in the range from about 5 to 40 lb/100 ft2, preferably from about 10 to ~5 lb/100 ft2 _ each determined at 50C. For the determination of these parameters, for the measuring methods used therein and for the rest of the usual composition of the invert drilling fluids described here, the details apply as in the prior art, cited above and described in detail, for example, in the "Manual of Drilling Fluids Technoloqy" of the CQmpany ML Baroid, London, GB, and in particular under the chapter "Mud Testing - Tbols and Technique~" and "Oil Mud Technology" which is freely accessible to interested experts. In sumnary for the purposes of completion of the invention disclosure the follc~ing can be said:
The emulsifiers that can be used in practice are syst~ms suitable for the formation of the required ~/O-emulsions. In particular, selected oleophilic fatty acid salts, e.g. those based on amidoam m e compounds, can be considered.
Examples of these are described in US PS 4,374,737 and the literature cited therein. A particularly suitable type of emLlsifier is the product sold by the cc~pany NL Baroid under the brand name "EZ-mul".
Emulsifiers of this type are sold crmmercially as hic~hly-concentrated acti~e substan oe preparations and can, for e~ample, be used in amounts from about 2.5 to 5 % by weight, particularly in amounts from about 3 to 4 ~ ~y ~eic~ht - referred to the oil phase.
~ydrophobized lignite particularly is used in practice as the fluid-1068 additive and thus in particular to form a d~n6e ooating -of a : , .
., ., ~ ~ ~ 7 !~ q _ 9 _ largely liquid-impermeable film on the bore-hole ~alls. Suitable amounts lie in the range, for example, frQm about 15 to 20 Ib/bbl or from about 5 to 7 ~ by weight, referred to the oil phase.
Barite is the weighting agent generally used in relevant applications to establish the necessary pressure compensation, the amounts added being varied according to the drilling conditions to be anticipated in each case. By adding barite, it is, for example, possible to raise tne specific weight of the drilling fluid to 2.S and preferably to a value in the range of about 1.3 to 1.6.
The dispersed aqueous phase in these invert drilling fluids is loaded with soluble salts. Calcium chloride and/or potassium chloride are used predaminantly here, saturation of the aqueous phase at room temperature with the soluble salt being preferred.
The aforementioned emulsifiers, or emulsifier systems, optionally also serve to improve the oil wettability of the inorganic weighting materials. In addition to the amL~Damides already mentioned, further examples are alkylbenzene sulfonates and imidazoline conpounds.
Additional information regarding the relevant Prior ~rt can be found in the following publications: GB 2 158 437, EP 229 912 and DE 32 47 123.
:
7 ~
E x a m p 1 e s Example 1 200 g of coTmercial hydrotalcite is suspended in one liter of i-propanol. 132 g of lauric acid is dissolved as far as possible in one liter of i-propanol and added to the hydrotalcite suspension. The resulting suspension is stirred for four hours at -oom temperature and then refluxed for one hour. Afterwards the solids are îiltered off, washed with i-propanol and dried at 110C in the drying cabinet.
Example 2 200 g of cG~mercial hydrotalcite is suspended in one liter of i-propanol. 187 g of stearic acid is dissolved as far as possible in one liter of i-propanol and added to the hydrotalcite suspension. me resulting suspension is stirred for four hours at room temperature and then refluxed for one hour. Afterwards the solids are filtered off, washed with i-propanol and dried in the drying cabinet at 110C.
Example 3 315.5 g of an industrial colza-oil/split fatty acid mlxture is mLxed and stirred with 400 g of o~mmercial hydrotalcite. The semi-solid, crumbly product is after-dried in the drying cabinet at 110C.
Example 4 1S5.6 g of an industrial colza-oil/split fatty acid mLxture i6 mixed and stirred with 400 g of oom~ercial hydrotalcite. The semi-solid, crumbly product is after-dried in the drying cabinet at 110C.
EKamPle 5 A mLXture of 22.5 g of Al(OH)3 and 100 g of zinc stearat~ is melted at125 to 130C and held for an hour at this temperature. ~he oooled solidified melted material is then ground to powder.
Example 6 100 g of ocmmercial hydrotalcite is suspended in one liter of water ~nd 67.2 g of dodecyIbenzenesulfonic acid i8 add~d. The suspension i~
stirred for one hour at room temperature, the solid matter i8 drawn off, washed with water and dried.
Example 7 1800 ml of water i9 mlxed with 200 g of an industrial colza-oilJsplit fatty acid mixture and with 500 g of a 50 ~ by weight sodium hydroxide solution. A solution of 230 g of magnesium nitrate/hexahydrate and 169 g of aluminium-nitrate-nonahydrate in 630 g of water is allowed to drop into this muxture under stirring at room temperature (fcam formationl).
After the addition is complete, stirring is continued for four hours at 65C, the solid matter was drawn off, washed with water and dried at 110C in the drying cabinet.
Ex1mple 8 A solution is prepared of 410 g of magnesium nitrate/hexahydrate and300 g of aluminium nitrate/nonahydrate in 8000 g of totally deionized water and a second solution is prepare from 448 g of 50 ~ sodium hydroxide solution and 160 g of scdium car~onate (water free) in 8000 g of totally deionized water. The two solutions are pumped with peristaltic (hose) pumps through the leg of a Y-shaped tube into a receiver, the hydrotalcite precipitate fonmed is dra~n off and washed with totally deionized water. m e pasty product with a solids content of a maximu~ of 70 ~ (determlned by drying at 110C) is not dried further so that the fine primary particles do not aggl~merate further.
100 g of the acove paste with a solids content of about 25 % by weight is suspended in 250 ml of fully deionized water and mlxed at room temperature with 2.5 g of phosphonoacetic acid monoethylester. The mlxture is stirred, filtered, washed ~ith water and dried at 110 in the drying cabinet.
Example 9 100 g of the hydrotalcite paste from Example 8 is suspended in 250 ml of fully dei~niæed water and muxed at room temperature with 5 g of 12-hydroxystearic acid. The mixture is stirred for one hour at room temperature, filtered, washed with water and dried at 110C in the drying cabinet.
Example 10 Rheology-regulating additive~ according to the invention and state-of-the-art comparati~e produ~ts were tested in a diesel drilling fluid with the follcwing formulation:
168 g diesel oil 6 g W/0-emLlsifier ~"Invermul~ of the oompany NL Baroid) - 12 - `` ' "`' `~
3 g lime 6 g organophilic lignite ("Duratone" of the ooTpany NL Bar~id) 3 g W/0-emulsifier ("EZ-mul NT" of the coTpany NL Baroid) 73 g CaC12-solution 470 g barite ____________________ 2 g rheology-regulating additive according to the table below As the test parameters, the following were measured: Plastic viscosity(PV) in cP and yield point (YP) in lb/100 ft2 and the gel streng~h (GS) in lb/100 ft2 for 10 sec. and 10 mun., in which in each case the first figure in the table refers to the value after the production of the fluid, the seoond figure refers to the value after ageing (16 hours) at 250F.
Additive from Example No. PV YP GS
___________.________________________________________________________ 1 41 / 3510 ~ 7 4;5 ~ 4;6 2 43 / 361~ / 13 5;6 / 5j6 4 42 / 4114 / 11 5;6 ~ 5;6 43 / 4310 / 11 4;5 / 5;6 6 42 / 42~ / 11 4;5 / 5;7 7 43 / 4311 / 8 5;6 / 5;6 8 40 / 351~ / 11 4;4 / 4;5 9 41 / 411~ / 14 4;4 ~ 5;6 Geltone II
(oomparison) 50 / 453'3 J 39 15;18 / 15;19 Cmnigel (oomparison) 47 / 4419 / 41 8;11 / 16;21 Perchem (comparison) 50 / 4521 / 42 8;10 / 16;20 .
, .~ .
Claims (20)
1. Agents for influencing the rheology, in particular for the controlled increase in the viscosity, of non-aqueous liquid phases based on hydrophobic oil-dispersible mixed-hydroxide compounds of inorganic basic structure, characterized in that they are formed at least in part by finely dispersed particles of inorganic layered compounds with a positive layer charge based on two-dimensional inorganic polycations (polycationic layered compounds) and mono- and/or polybasic acid anions of marked oleophilic character.
2. Agents according to claim 1 characterized in that they contain, as the polycationic layered compounds, mixed hydroxo salts of divalent and trivalent metal ions.
3. Agents according to claims 1 and 2, characterized in that they contain hydrophobic finely dispersed mixed hydroxide compounds of the following general formula I
M(II)1-xM(III)x(CH)2Ax ? nH2O (I) in which M(II) represents at least one divalent metal ion, M(III) represents at least one trivalent metal ion and A represents an equivalent of anions of mono- and/or polybasic acids at least partly of a marked oleophilic character and x signifies a number from 0.01 to 0.5 and n signifies a number from 0 to 20, such that at least such a part of the radical A derives from corresponding acids of marked oleophilic character that the solids of the general formula I are hydrophobic.
M(II)1-xM(III)x(CH)2Ax ? nH2O (I) in which M(II) represents at least one divalent metal ion, M(III) represents at least one trivalent metal ion and A represents an equivalent of anions of mono- and/or polybasic acids at least partly of a marked oleophilic character and x signifies a number from 0.01 to 0.5 and n signifies a number from 0 to 20, such that at least such a part of the radical A derives from corresponding acids of marked oleophilic character that the solids of the general formula I are hydrophobic.
4. Agents according to claims 1 to 3, characterized in that they contain solids of the general formula I, in which M(II) represents magnesium, calcium, barium and/or zinc, and M(III) represents aluminium and/or iron.
5. Agents according to claims 1 to 4, characterized in that they contain solids of the general formula I, in which as the hydrophobizing radica A, anions of oleophilic organic compounds with at least one salt-forming acid group, preferably from the class of carboxyl groups and/or hetero-organic acid radicals, particularly based on sulphur and/or phosphorus, are present, such that in the case of polybasic acid groups the anion-forming acid radical can also be linked to the oleophilic organic radical by hetero-atoms.
6. Agents according to claims 1 to 5, characterized in that they contain solids of the general formula I, in which the hydrophobizing anionic acid radicals A are derived from compounds of the general formulae R-X (IIa) and/or R-O-Y (IIb), such that in these formulae X represents a -COOH, -SO3H or -PO3HR' group and R
signifies a hydrocarbon radical with at least six carbon atoms and R' signifies hydrogen or an alkyl radical with 1 to 20 carbon atoms.
signifies a hydrocarbon radical with at least six carbon atoms and R' signifies hydrogen or an alkyl radical with 1 to 20 carbon atoms.
7. Agents according to claims 1 to 6, characterized in that they contain solids of the general formula I in conjunction with the general formulae IIa and/or IIb, in which R represents a linear or branched, saturated or unsaturated alkyl or arylalkyl radical, which can also be substituted with hydroxyl, thiol and/or amino groups.
8. Agents according to claims 1 to 7, characterized in that they contain solids of the general formula I in conjunction with the general formulae IIa and/or IIb, in which the radical R contains 8 to 36 carbon atoms.
9. Agents according to claims 1 to 8, characterized in that in the compounds of the general formula I the anionic radical A is derived from environmentally acceptable compounds of low toxicity.
10. Use of the agents according to claims 1 to 9 in non-aqueous liquid phases, particularly as structure formers and viscosity regulators.
11. Embodiment according to claim 10, characterized in that the agents can be used in W/O-emulsions in particular as gelling agents that increase viscosity in W/O-invert drilling fluids with a continuous oil phase.
12. Process for the production of compounds of the general formula I, characterized in that in the pre-formed polycationic layer compounds according to this formula I, in which the radical A, however, has a different meaning from that in the definition according to the invention, the mono- and polybasic acid anions of marked oleophilic character are introduced in a manner known per-se by an after-treatment, or the compounds of the general formula I are obtained by direct reaction of all the reactants in the melt or in the preferred alkaline solution.
13. Process according to claim 12, characterized in that the hydrophobizing acid anions of marked oleophilic character are introduced particularly in the synthesis in the melt as the salt of the di- and/or trivalent metals used and there react with the residual reactants preferably present in hydroxide form.
14. Process according to claim 12, characterized in that during the reaction in a solvent - preferably on an aqueous base - salts and/or hydroxides of the divalent and trivalent metals are reacted with the salts, preferably the alkali salts of the mono-and/or polybasic acids of marked oleophilic character.
15. W/O-invert drilling fluids, which are suitable for the development of, for example, petroleum or natural gas deposits and contain in a continuous oil phase a dispersed aqueous phase together with the usual auxiliary agents such as emulsifiers, weighting agents, fluid-loss additives and ideally further additional substances, characterized in that they contain as viscosity-regulating gelling agents at least in part the agents according to claims 1 to 9.
16. Drilling fluids according to claim 15, characterized in that they contain as the oil phase, so-called non-polluting oils, particularly from the class of at least largely aromatic-free hydrocarbon compounds, ester oils, alcohols and/or ethers.
17. Drilling fluids according to claims 15 and 16, characterized in that they contain as ecologically-acceptable oils at least in part ester oils in particular of monocarboxylic acids and mono- and/or difunctional alcohols, which are fluid and pumpable in the temperature range of 0 to 5°C and have flash points above 80°C.
18. Drilling fluids according to claims 15 to 17, characterized in that they have a plastic viscosity (PV) in the range from about 10 to 60 mPa.s and a yield point (YP) in the range from about 5 to 40 lb/100 ft2 - each determined at 50°C.
19. Drilling fluids according to claims 15 to 18, characterized, in, that their dispersed water part constitutes about 5 to 45 % by weight, preferably about 10 to 25 % by weight and contains in solution in particular salts of the type CaC12 and/or KCl.
20. Drilling fluids according to claims 15 to 19, characterized in that the oil phase of the invert drilling fluids in the temperature range of 0 to 5°C has a Brookfield (RVT) viscosity below 50 mPa.s, preferably not above 40 mPa.s.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3914916A DE3914916A1 (en) | 1989-05-06 | 1989-05-06 | AGENTS FOR BUILDING VISCOSITY IN NON-AQUEOUS LIQUID PHASES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3914916.1 | 1989-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2057024A1 true CA2057024A1 (en) | 1990-11-07 |
Family
ID=6380202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002057024A Abandoned CA2057024A1 (en) | 1989-05-06 | 1990-04-27 | Agent for increasing viscosity in non-aqueous fluid phases, process of making it and its use |
Country Status (9)
| Country | Link |
|---|---|
| EP (2) | EP0396983A1 (en) |
| JP (1) | JPH04505173A (en) |
| AU (1) | AU631427B2 (en) |
| BR (1) | BR9007350A (en) |
| CA (1) | CA2057024A1 (en) |
| DE (1) | DE3914916A1 (en) |
| TR (1) | TR24430A (en) |
| WO (1) | WO1990013608A1 (en) |
| ZA (1) | ZA903415B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109312220A (en) * | 2016-03-17 | 2019-02-05 | 沙特阿拉伯石油公司 | Contain oil base drilling fluid of the alkali earths adamantane compound as rheology modifier |
| WO2019036289A1 (en) * | 2017-08-15 | 2019-02-21 | Saudi Arabian Oil Company | Layered double hydroxides for oil-based drilling fluids |
| US10640696B2 (en) | 2017-08-15 | 2020-05-05 | Saudi Arabian Oil Company | Oil-based drilling fluids for high pressure and high temperature drilling operations |
| US10647903B2 (en) | 2017-08-15 | 2020-05-12 | Saudi Arabian Oil Company | Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers and amino amides as emulsifiers |
| CN111448284A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Oil-based drilling fluid compositions comprising layered double hydroxides as rheology modifiers |
| CN111448286A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Layered double hydroxide for oil-based drilling fluids |
| US10870788B2 (en) | 2017-08-15 | 2020-12-22 | Saudi Arabian Oil Company | Thermally stable surfactants for oil based drilling fluids |
| US10876039B2 (en) | 2017-08-15 | 2020-12-29 | Saudi Arabian Oil Company | Thermally stable surfactants for oil based drilling fluids |
| US10954425B2 (en) | 2017-08-15 | 2021-03-23 | Saudi Arabian Oil Company | Oil-based drilling fluids for high pressure and high temperature drilling operations |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4224537A1 (en) * | 1992-07-27 | 1994-02-03 | Henkel Kgaa | Mineral additives for adjusting and / or regulating the rheology and gel structure of aqueous liquid phases and their use |
| DE4410727A1 (en) * | 1994-03-28 | 1995-10-05 | Sued Chemie Ag | Thickener based on at least one synthetic layered silicate |
| US6462096B1 (en) * | 2000-03-27 | 2002-10-08 | Elementis Specialties, Inc. | Organophilic clay additives and oil well drilling fluids with less temperature dependent rheological properties containing said additives |
| WO2004010960A1 (en) * | 2002-07-25 | 2004-02-05 | Amcol International Corporation | Viscous compositions containing hydrophobic liquids |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287086A (en) * | 1975-05-02 | 1981-09-01 | Nl Industries, Inc. | Viscous organic systems containing an organophilic clay gellant without an organic dispersant therefor |
| EP0063631B1 (en) * | 1981-04-29 | 1985-09-04 | Kyowa Chemical Industry Co., Ltd. | Detergent-dispersant composition for lubricating or fuel oils |
| US4508628A (en) * | 1983-05-19 | 1985-04-02 | O'brien-Goins-Simpson & Associates | Fast drilling invert emulsion drilling fluids |
-
1989
- 1989-05-06 DE DE3914916A patent/DE3914916A1/en not_active Withdrawn
-
1990
- 1990-04-27 EP EP90108075A patent/EP0396983A1/en not_active Withdrawn
- 1990-04-27 AU AU55438/90A patent/AU631427B2/en not_active Ceased
- 1990-04-27 EP EP90906932A patent/EP0471705A1/en active Pending
- 1990-04-27 CA CA002057024A patent/CA2057024A1/en not_active Abandoned
- 1990-04-27 BR BR909007350A patent/BR9007350A/en not_active Application Discontinuation
- 1990-04-27 WO PCT/EP1990/000683 patent/WO1990013608A1/en not_active Application Discontinuation
- 1990-04-27 JP JP2506568A patent/JPH04505173A/en active Pending
- 1990-05-04 TR TR90/0411A patent/TR24430A/en unknown
- 1990-05-04 ZA ZA903415A patent/ZA903415B/en unknown
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109312220A (en) * | 2016-03-17 | 2019-02-05 | 沙特阿拉伯石油公司 | Contain oil base drilling fluid of the alkali earths adamantane compound as rheology modifier |
| CN109312220B (en) * | 2016-03-17 | 2021-03-09 | 沙特阿拉伯石油公司 | Oil-based drilling fluid containing alkaline earth adamantane compound as rheology modifier |
| CN111448287A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Layered double hydroxide for oil-based drilling fluids |
| US10647903B2 (en) | 2017-08-15 | 2020-05-12 | Saudi Arabian Oil Company | Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers and amino amides as emulsifiers |
| CN111448284A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Oil-based drilling fluid compositions comprising layered double hydroxides as rheology modifiers |
| CN111448286A (en) * | 2017-08-15 | 2020-07-24 | 沙特阿拉伯石油公司 | Layered double hydroxide for oil-based drilling fluids |
| US10640696B2 (en) | 2017-08-15 | 2020-05-05 | Saudi Arabian Oil Company | Oil-based drilling fluids for high pressure and high temperature drilling operations |
| US10745606B2 (en) | 2017-08-15 | 2020-08-18 | Saudi Arabian Oil Company | Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers |
| US10793762B2 (en) | 2017-08-15 | 2020-10-06 | Saudi Arabian Oil Company | Layered double hydroxides for oil-based drilling fluids |
| US10870788B2 (en) | 2017-08-15 | 2020-12-22 | Saudi Arabian Oil Company | Thermally stable surfactants for oil based drilling fluids |
| US10876039B2 (en) | 2017-08-15 | 2020-12-29 | Saudi Arabian Oil Company | Thermally stable surfactants for oil based drilling fluids |
| WO2019036289A1 (en) * | 2017-08-15 | 2019-02-21 | Saudi Arabian Oil Company | Layered double hydroxides for oil-based drilling fluids |
| US10954425B2 (en) | 2017-08-15 | 2021-03-23 | Saudi Arabian Oil Company | Oil-based drilling fluids for high pressure and high temperature drilling operations |
| US10988659B2 (en) | 2017-08-15 | 2021-04-27 | Saudi Arabian Oil Company | Layered double hydroxides for oil-based drilling fluids |
| US11034880B2 (en) | 2017-08-15 | 2021-06-15 | Saudi Arabian Oil Company | Oil-based drilling fluids for high pressure and high temperature drilling operations |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0396983A1 (en) | 1990-11-14 |
| ZA903415B (en) | 1991-01-30 |
| WO1990013608A1 (en) | 1990-11-15 |
| TR24430A (en) | 1991-11-01 |
| JPH04505173A (en) | 1992-09-10 |
| DE3914916A1 (en) | 1990-11-08 |
| EP0471705A1 (en) | 1992-02-26 |
| AU631427B2 (en) | 1992-11-26 |
| BR9007350A (en) | 1992-04-21 |
| AU5543890A (en) | 1990-11-29 |
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