EP0471705A1 - Agents d'etablissement de la viscosite dans des phases liquides non aqueuses, procede de preparation et applications - Google Patents

Agents d'etablissement de la viscosite dans des phases liquides non aqueuses, procede de preparation et applications

Info

Publication number
EP0471705A1
EP0471705A1 EP90906932A EP90906932A EP0471705A1 EP 0471705 A1 EP0471705 A1 EP 0471705A1 EP 90906932 A EP90906932 A EP 90906932A EP 90906932 A EP90906932 A EP 90906932A EP 0471705 A1 EP0471705 A1 EP 0471705A1
Authority
EP
European Patent Office
Prior art keywords
compounds
general formula
agents
drilling fluids
contain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP90906932A
Other languages
German (de)
English (en)
Inventor
Helmut Endres
Heinz Müller
Claus Peter Herold
Angela Hansen
Günter GEISMAR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0471705A1 publication Critical patent/EP0471705A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—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

Definitions

  • the invention relates to new possibilities for influencing and controlling the rheology of non-aqueous liquid phases and in particular enables a controlled viscosity build-up in liquids of this type.
  • non-aqueous drilling fluids based on so-called invert drilling fluids, which are widely used today and which contain a disperse aqueous phase in a closed oil phase.
  • An important area of use for such drilling mud systems is offshore drilling for the development of oil and / or gas deposits.
  • Today such W / O emulsions are also used as drilling irrigation systems, but also very generally for land-based drilling, for example for geothermal drilling, for water drilling, for performing geoscientific drilling and for drilling in the mining sector.
  • the invention relates to improved drilling fluids of this type of W / O invert system, so that reference is made in particular to this area of use in the following, although the invention is in no way restricted to this.
  • hydrophobic layered silicates are used as rheology-regulating additives for non-aqueous drilling fluids from the group of bentonites.
  • Such products are commercially available, for example, under the collective name "Bentone”.
  • the surface hydrophobization required for incorporation into the slightly to non-polar carrier liquid is usually carried out using quaternary ammonium salts, the organic cations of which combine with the negatively charged layered silicate platelets via electrostatic interactions.
  • quaternary ammonium salts used for hydrophobizing generally have biocidal effects, so that environmental damage cannot be ruled out.
  • the object of the invention is to provide substitutes for influencing and controlling the rheology of such non-aqueous liquid phases that are less ecologically conceivable, but at least equivalent in technical practice.
  • the technical solution to this problem is based on the knowledge that selected inorganic layer materials with a positive stratified charge (inorganic polycations) which have been brought to interact with 1- and / or polybasic acid anions with a pronounced oleophilic character are at least equivalent as rheology / regulating additives Results deliver like the usual hydrophobized bentonite compounds.
  • the invention relates, in a first embodiment, to agents for influencing the rheology, in particular for the controlled viscosity build-up of non-aqueous liquid phases based on hydrophobic oil-dispersible mixed hydroxide compounds of an inorganic basic structure, the characterizing feature of the invention being that these agents are used at least partly by finely dispersed particles of inorganic layered compounds with positive layer charge based on 2-dimensional inorganic polycations (polycationic Layered compounds) and 1- and / or polybasic acid anions of pronounced oleophilic character are formed.
  • x is a number from 0.01 to 0.5 and n is a number from 0 to 20.
  • hydrota-conductive layer compounds by treatment with anionic surface-active agents.
  • DE-PS 30 19 632 mentions that hydrotalcite treated in this way is particularly suitable for stabilizing halogen-containing plastics.
  • this does not anticipate the use according to the invention of the reaction products of inorganic polycationic layer materials with acid anions of pronounced oieophilic character for influencing and controlling the rheology of non-aqueous liquid phases, in particular in the sense of a controlled viscosity build-up.
  • EP-OS 207 811 describes the use of non-hydrophobized mixed metal hydroxides, which are particularly finely divided by a complex process, in aqueous drilling fluids.
  • the invention aims to influence non-aqueous liquid phases in their rheology. This requires the hydrophobization of the polycationic layer compounds provided according to the invention through the incorporation of the 1- and / or the polybasic acid anions with a pronounced oophilic character into the polycationic inorganic material.
  • the mixed hydroxy salts of divalent and trivalent metal ions provided according to the invention form hydrophobic, finely dispersed solids of the following general formula I.
  • M (II) for at least one divalent metal ion M (III) for at least one trivalent metal ion and A for one equivalent of anions of 1- and / or polybasic acids are at least partly pronounced in an oophilic character and x is a number of 0, 01 to 0, 5 and n are a number from 0 to 20, where at least such a portion of the radical A is derived from corresponding acids with a pronounced oophilic character that the solids of the general formula I are hydrophobic.
  • Hydrophobic behavior is already evident when 2 to 3% by weight (based on the total amount of the solid) is incorporated into an acid anion with a pronounced oleophilic character.
  • hydrophobic is understood to mean a solid which, in the following test, is more than 90% dispersed in the oil phase: 1 g of the test substance is placed in 50 ml demineralized water in a 100 ml beaker. The aqueous phase is covered with 5 ml of silicone oil (for example the commercial product "Baysilon 100" from B VYER AG) and the two phases are mixed by stirring with a magnetic stirrer. The hydrophobic portion of the solid is dispersed in the oil phase, which can clump together when the solid is heavily loaded and sink downward.
  • silicone oil for example the commercial product "Baysilon 100" from B VYER AG
  • the divalent metal ions M (II) from the formula I are formed by magnesium, calcium, barium or zinc or by any mixtures thereof.
  • the invention is not restricted to this.
  • any divalent metal ions can be used, such as those in one wider framework are disclosed for example in the already mentioned EP-OS 207 811.
  • the preferred metal ions M (I I I) from the compounds of the general formula I are aluminum and / or iron in the sense of the invention.
  • these trivalent metal ions can be used in a broader range, as disclosed, for example, in the European patent application mentioned.
  • radical A from the general formula I which is formed at least in part by the hydrophobizing acid radicals.
  • These are anions of oleophilic organic compounds with at least one salt-forming acid group.
  • a suitable acid group of this type is the carboxyl group.
  • the invention is not limited to this.
  • residues of heteroorganic acids are also suitable, with heteroorganic acids based on sulfur and / or phosphorus being particularly suitable.
  • the following also applies here: v
  • the acid grouping can attack the oieophilic base structure directly with the respective core of the acid group.
  • the anion-forming acid residue can also be bound to the oieophilic organic residue via heteroatoms, for example oxygen.
  • This last embodiment is particularly important for polybasic acids such as sulfonic acids or phosphonic acids, which can then also be used in the form of their acidic esters of pronounced oophilic character.
  • agents of general formula I apply in preferred embodiments are compounds in which the hydrophobizing anionic acid residues A are derived from compounds RX (l la) and / or from compounds of the formula ROY (l lb), where the following applies to these two general formulas:
  • R stands for a pronounced oieophilic hydrocarbon radical with preferably at least 6 carbon atoms
  • X stands for the anionic radicals of the acid group, which can preferably be derived from -COOH, -SO.H and / or -PO-HR '.
  • Y is the anionic radical of -SO, H or -PO, HR ', where in these cases R 1 can in each case mean hydrogen or a hydrocarbon radical - in particular an alkyl radical - with, for example, up to 20 C atoms.
  • Particularly suitable acid anions A from the general formula I are derived from acids which come under the general formulas I la and / or Ib, the radical R here in each case being a linear or branched, saturated or unsaturated alkyl and / or arylalkyl radical stands. These pure hydrocarbon residues can also be substituted. Suitable substituents are in particular hydroxyl, thiol and / or amino groups. A particularly preferred meaning for the radical R s and hydrocarbon radicals of the type specified above with 8 to 36 C atoms. Appropriate carboxylic acids of natural and / or synthetic origin can be particularly suitable here, carbonic acid mixtures of natural origin being particularly important. All of these are hydrophobizing anionic radicals A in the general formula I, which are derived from environmentally compatible compounds of low toxicity and thus do justice to this aspect of the task according to the invention.
  • the invention comprises methods for producing the means and in particular of finely dispersed compounds of the general formula I. There are basically several ways to do this:
  • polycationic layer compounds of the type specified are first produced in a manner known per se, but in which the intra-crystalline charge compensation is effected by anions which differ in their constitution from the anionic radicals A defined in general formula I according to the invention .
  • Both inorganic and organic acid residues come into consideration here, the salt-forming acid residues from the metal salts used for the synthesis of the double-layer hydroxides generally being present.
  • the mixed hydroxide compounds obtained initially are then treated with the selected 1- and / or polybasic acids with a pronounced oieophilic character and / or their salts soluble in the reaction medium. At least an enveloping hydrophobization of the polycationic inorganic layer materials occurs with salting.
  • Hydroxo salts of this type are then oil-dispersible and can be used for rheology control in the sense of the invention.
  • liquid phases are used, for example, as follows: an alkaline solution of the hydrophobicizing acid, for example an alkanoic acid or an alkane acid mixture, is mixed with a solution of the divalent and trivalent metal cations in the required molar ratio .
  • a liquid phase or Solvents can be used in water and / or aqueous-organic liquid phases.
  • the formation of the mixed hydroxy salt is then effected in this system, for example by heating. Details can be found in the cited prior art for the formation of double-layer hydroxides of the type concerned here.
  • Another and particularly suitable synthetic route consists in reacting the hydroxide (s) of the one metal component (s) - that is, for example, the bivalent metal components - with an easily meltable salt of the further required metal component (s) in the melt , whereby these last-mentioned metal salts already contain the 1 - and / or polybasic acid anions with a pronounced oieophilic character as a salt-forming component.
  • the reactants After the reactants have reacted in the melt, the cooled melt is then ground.
  • the invention comprises the use of the agents described in the beginning in non-aqueous liquid phases, in particular as structuring agents and viscosity adjusting agents. It is particularly important in the context of the invention to use these agents as rheology-modifying agents in W / O invert drilling fluids with a closed oil phase and disperse aqueous phase.
  • W / O invert drilling fluids of the last-mentioned type fall within the scope of the invention, which are characterized in that, as a rheology-modifying agent, they at least partially include the previously described agents of the invention, in particular of the general formula I contain .
  • Drilling fluids of this type consist of a 3-phase system: oil, water and finely divided solids.
  • a plurality of additives are provided, in particular emulsifiers, weighting agents, fluid loss additives, alkali reserves, viscosity regulators and the like.
  • Selected diesel oil fractions are used as the oil phase, and in particular, in recent times, at least largely aromatic-free pure hydrocarbon oils have been used.
  • the relevant technology has for some time recognized the importance of the environmental problems caused by these oil phases. This explains the increasing importance of oil rinsing based on so-called nonpolluting oils.
  • oil phases based on ester are also included in the class of nonpolluting oils. Useful and precisely improved from the point of view of environmental protection ester oils or invert drilling fluid systems based on ester oils are the subject of a number of earlier applications by the applicant.
  • the structure-forming gel formers described according to the invention can advantageously be used in all of these materials.
  • the amount of the viscosity formers used according to the invention corresponds approximately to the amounts of the components used hitherto based on cationically modified finely divided bentonites. Additive amounts are therefore particularly suitable in the range from approximately 0.5 to 5% by weight, preferably in the range from approximately 0.8 to 3.5% by weight, based on the oil phase.
  • Invert drilling muds of the type concerned usually contain, together with the closed oil phase, the finely disperse aqueous phase in amounts of about 5 to 45% by weight and preferably in amounts of about 5 to 25% by weight.
  • the range from about 10 to 25% by weight of disperse aqueous phase can be of particular importance.
  • plastic Viscosity in the range from about 10 to 60 mPas, preferably from about 15 to 40 Pas
  • yield point in the range from about 5 to 40 lb / 100 ft, preferably from about 10 to 25 lb / 100 ft. each determined at 50 ° C.
  • Emulsifiers which are useful in practice are systems which are suitable for forming the required W / O emulsions, in particular selected oleophilic fatty acid salts, for example those based on amidoamine compounds, are suitable.
  • Emulsifiers of the type concerned here are sold commercially as highly concentrated active ingredient preparations and can be used, for example, in amounts of about 2.5 to 5% by weight, in particular in amounts of about 3 to 4% by weight, based in each case on the oil phase Find .
  • liquid-impermeable film is used in particular hydrophobized lignite.
  • Suitable amounts are, for example, in the range from about 15 to 20 lb / bbl or in the range from about 5 to 7% by weight, based on the oil phase.
  • the weighting agent usually used in the relevant practice for setting the required pressure equalization is barite, the additional amounts of which are adapted to the respectively expected conditions of the bore. For example, by adding barite, it is possible to increase the specific weight of the drilling fluid to values in the range up to approximately 2.5 and preferably in the range from approximately 1.3 to 1.6.
  • the disperse aqueous phase is loaded with soluble salts in invert drilling fluids of the type concerned here.
  • Calcium chloride and / or potassium chloride are predominantly used here, the saturation of the aqueous phase at room temperature with the soluble salt being preferred.
  • emulsifiers or emulsifier systems may also serve to improve the oil wettability of the inorganic weighting materials.
  • further examples are alkylbenzenesulfonates and imidazoline compounds. Additional information on the relevant prior art can be found in the following references: GB 2 158 437, EP 229 912 and DE 32 47 123.
  • a mixture of 22.5 g of Al (OH) and 100 g of zinc stearate is melted at 125 to 130 ° C. and kept at this temperature for one hour. The cooled melt cake is then ground.
  • a solution of 410 g of magnesium nitrate hexahydrate and 300 g of aluminum nitrate nonahydrate in 8000 g of fully deionized (VE) water and a second solution of 448 g of 50% by weight are prepared.
  • -% Sodium hydroxide solution and 160 g sodium carbonate (anhydrous) in 8000 g demineralized water are prepared.
  • the two solutions are pumped with peristaltic pumps through the legs of a Y-shaped tube into a collecting vessel, the hydrotalcite precipitate formed is suctioned off and washed with demineralized water.
  • the pasty product with a solids content of at most 70% by weight is not further dried, so that the fine primary particles do not agglomerate further.
  • 100 g of the above paste with a solids content of about 25% by weight are slurried in 250 ml of demineralized water and 2.5 g of phosphonoacetic acid monoethyl ester are added at room temperature. The mixture is stirred for one hour at room temperature, filtered, washed with water and dried at 110 ° C. in a drying cabinet.
  • hydrotalcite paste from Example 8 100 g of the hydrotalcite paste from Example 8 are slurried in 250 ml of deionized water and 5 g of 12-hydroxystearic acid are added at room temperature. The mixture is stirred for one hour at room temperature, filtered, washed with water and dried at 110 ° C. in a drying cabinet.

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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

On décrit des agents permettant d'influencer la rhéologie, et en particulier de contrôler l'établissement de la viscosité de phases liquides non aqueuses à base d'hydroxydes mixtes hydrophobes et pouvant se disperser dans l'huile, à structure de base inorganique, caractérisés en ce qu'ils sont constitués au moins en partie de particules finement dispersées de composés inorganiques en couche avec une charge de couche positive à base de polycations inorganiques à deux dimensions (composés polycationiques en couches) et de un ou plusieurs anions à plusieurs bases, à caractère nettement oléophile. L'invention concerne également des procédés pour la fabication de ces agents. Dans un autre mode d'exécution, on décrit l'utilisation de ces agents dans des phases liquides non aqueuses, en particulier en tant qu'éléments produisant des gels pour l'établissement de la viscosité dans des fluides de forage à circulation inverse du type eau dans l'huile avec une phase huile fermée, ainsi que la constitution de ces fluides de forage.
EP90906932A 1989-05-06 1990-04-27 Agents d'etablissement de la viscosite dans des phases liquides non aqueuses, procede de preparation et applications Pending EP0471705A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3914916 1989-05-06
DE3914916A DE3914916A1 (de) 1989-05-06 1989-05-06 Mittel zum viskositaetsaufbau in nichtwaessrigen fluessigphasen, verfahren zu ihrer herstellung und ihre verwendung

Publications (1)

Publication Number Publication Date
EP0471705A1 true EP0471705A1 (fr) 1992-02-26

Family

ID=6380202

Family Applications (2)

Application Number Title Priority Date Filing Date
EP90108075A Withdrawn EP0396983A1 (fr) 1989-05-06 1990-04-27 Fluides de forage, contenant des substances thixotropes formant un gel
EP90906932A Pending EP0471705A1 (fr) 1989-05-06 1990-04-27 Agents d'etablissement de la viscosite dans des phases liquides non aqueuses, procede de preparation et applications

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP90108075A Withdrawn EP0396983A1 (fr) 1989-05-06 1990-04-27 Fluides de forage, contenant des substances thixotropes formant un gel

Country Status (9)

Country Link
EP (2) EP0396983A1 (fr)
JP (1) JPH04505173A (fr)
AU (1) AU631427B2 (fr)
BR (1) BR9007350A (fr)
CA (1) CA2057024A1 (fr)
DE (1) DE3914916A1 (fr)
TR (1) TR24430A (fr)
WO (1) WO1990013608A1 (fr)
ZA (1) ZA903415B (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4224537A1 (de) * 1992-07-27 1994-02-03 Henkel Kgaa Mineralische Additive zur Einstellung und/oder Regelung der Rheologie und Gelstruktur wässriger Flüssigphasen und ihre Verwendung
DE4410727A1 (de) * 1994-03-28 1995-10-05 Sued Chemie Ag Verdickungsmittel auf der Basis mindestens eines synthetischen Schichtsilicats
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
MXPA05000970A (es) * 2002-07-25 2005-06-08 Amcol International Corp Composiciones viscosas que contienen liquidos hidrofobicos.
US10087355B2 (en) * 2016-03-17 2018-10-02 Saudi Arabian Oil Company Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier
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
US10676658B2 (en) 2017-08-15 2020-06-09 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
US10876039B2 (en) 2017-08-15 2020-12-29 Saudi Arabian Oil Company Thermally stable surfactants 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
US10793762B2 (en) * 2017-08-15 2020-10-06 Saudi Arabian Oil Company Layered double hydroxides for oil-based drilling fluids
JP2020531609A (ja) 2017-08-15 2020-11-05 サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ 油系掘削流体用の熱安定性界面活性剤
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

Family Cites Families (3)

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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 (fr) * 1981-04-29 1985-09-04 Kyowa Chemical Industry Co., Ltd. Composition détergente et dispersante pour huiles lubrifiantes et combustibles
US4508628A (en) * 1983-05-19 1985-04-02 O'brien-Goins-Simpson & Associates Fast drilling invert emulsion drilling fluids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9013608A1 *

Also Published As

Publication number Publication date
DE3914916A1 (de) 1990-11-08
ZA903415B (en) 1991-01-30
AU631427B2 (en) 1992-11-26
EP0396983A1 (fr) 1990-11-14
BR9007350A (pt) 1992-04-21
AU5543890A (en) 1990-11-29
WO1990013608A1 (fr) 1990-11-15
CA2057024A1 (fr) 1990-11-07
TR24430A (tr) 1991-11-01
JPH04505173A (ja) 1992-09-10

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