WO2007059941A1 - Utilisation de sels metalliques polyvalents pour stabiliser la rheologie de phases liquides - Google Patents

Utilisation de sels metalliques polyvalents pour stabiliser la rheologie de phases liquides Download PDF

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Publication number
WO2007059941A1
WO2007059941A1 PCT/EP2006/011193 EP2006011193W WO2007059941A1 WO 2007059941 A1 WO2007059941 A1 WO 2007059941A1 EP 2006011193 W EP2006011193 W EP 2006011193W WO 2007059941 A1 WO2007059941 A1 WO 2007059941A1
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WO
WIPO (PCT)
Prior art keywords
component
use according
mixed metal
rheology
liquid phase
Prior art date
Application number
PCT/EP2006/011193
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German (de)
English (en)
Inventor
Johann Plank
Jürgen HEIDLAS
Gregor Keilhofer
Peter Lange
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Basf Construction Polymers Gmbh
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Application filed by Basf Construction Polymers Gmbh filed Critical Basf Construction Polymers Gmbh
Publication of WO2007059941A1 publication Critical patent/WO2007059941A1/fr

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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
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/16—Clay-containing compositions characterised by the inorganic compounds other than clay
    • 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
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/032—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/05—Aqueous well-drilling compositions containing inorganic compounds only, e.g. mixtures of clay and salt
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/145—Clay-containing compositions characterised by the composition of the clay

Definitions

  • the present invention is the use of polyvalent metal salts to stabilize the rheology of liquid phases.
  • the thickening of water and oil based systems with the help of ultrafine swelling clays of natural or synthetic origin is a common measure and it is used in practice to a greater extent. Irrespective of the different fields of application, the shear-thinning and / or thixotropic thickening of the respective liquid phase is in the foreground. Especially widespread is the use of bentonite and especially those types of clay, which are characterized by a high proportion of sodium montmorillonite.
  • MMO mixed metal oxides
  • MMH mixed metal hydroxides
  • MMH-based fluids are very valuable in the field of drilling technology, since such drilling fluids efficiently support the necessary discharge of the cuttings in natural gas and oil wells.
  • MMO and MMH are well known to those skilled in the art and also sufficiently documented by the prior art.
  • MMO and MMH are often structurally scarcely characterized and defined only by very general and broad molecular formulas.
  • the actual definition of the terms mixed metal oxide (MMO) and mixed metal hydroxide (MMH) results therefore on the one hand on their synthesis route, on the other hand but also on their use and their effect in the particular combination with a clay component and in particular in connection with the rheology control of liquid phases. It is usually assumed that, irrespective of the description of the mischmetal component used in each case, a layer-structured mixed metal hydroxide of the general formula
  • M ll i- ⁇ M III x (OH) 2 ] (A n ) - ⁇ / n is present or the mixed metal hydroxide forms by hydration processes; M "and M '” stand for divalent or trivalent metal cations and A means any, but only loosely bound anion.
  • n is the charge of the anion and in particular -5 ⁇ n ⁇ -1.
  • x indicates these contents of M "and M '", and more specifically, 0 ⁇ x ⁇ 1, and more preferably 0 ⁇ x ⁇ 1.
  • the predominantly positively charged surfaces of these clay-like minerals can interact with conventional clays because of the properties described, forming adducts and network structures, which ultimately leads to an increase in the viscosity in the liquid phase.
  • WO 01/49406 describes, by way of example, the preparation of corresponding liquid phases based on clay and water and in particular using the mixed metal compounds of the general formula described there very broadly:
  • M ' is at least one divalent metal cation and m is a number greater than 0 to about 8; M "represents at least one trivalent metal cation and n is a number greater than 0 to about 6;
  • A represents an anion or a residue with negative charges, which may be monovalent or polyvalent;
  • a represents the number of ions A of valence q, wherein in the case of a monovalent A ion, a is greater than 0 to about 8; if A is polyvalent, a must be greater than 0 to about 4;
  • B has the meaning of a second or negative charge moiety which is monovalent or polyvalent b is the number of B ions of valence r, where b is a number from 0 to about 4, (m + n) must be ⁇ 1 and the sum of qa + br may not be greater than the sum 2m + 3n; furthermore, qa must not correspond to the sum 2m + 3n; another requirement is that the sum of (2
  • the formula given in WO 01/49406 covers in particular thermally activated and preferably calcined hydrotalcites, hydrotalcite-like compounds or mixtures thereof.
  • the calcination may, for example, have also occurred in the presence of sodium, and preferably at temperatures in the range between 900 and 1000 ° C.
  • As particularly preferred calcined mixtures of individual components are given, as obtained, for example, in the context of the processing of bauxite.
  • D is at least one divalent metal ion
  • d 0 to 6
  • T is at least one trivalent metal ion
  • A is different from OH ' and is a monovalent or polyvalent anion
  • a is the number A
  • n is the valence of A
  • na is ⁇ 0, (m + d)> 0, q ⁇ 0; the sum of (m + 2d + 3 + na)> 2.
  • M is Ca, Mg, Zn 1 Cu 1 Ba, Sr, Fe, Ni, Mn and / or Co
  • M" 1 is a member of the series AI, Fe, Co, Ni, Mn, Cr and Ga
  • A is a mono- and / or polyvalent anion with the valency n ⁇ 0, with hydroxide, halide, sulfate, nitrate, carbonate, silicate, phosphate and / or borate being preferred
  • x 0.2 to 0.5 and q> 0.
  • the mixed metal hydroxides together with bentonite form adducts
  • the mixed metal hydroxides described therein together with hectorite form adducts which are respectively suitable for rheology control of liquid phases.
  • the disclosures in these documents relating to the mixed metal hydroxides are substantive components of the present invention.
  • U.S. Patent 6,906,010 describes formulations for rheology modification in liquids useful in oil and gas drilling, as well as in oil and gas drilling
  • Tunneling can be used.
  • aqueous fluids with rheology-modifying properties contain clay, water,
  • Liquid phases based on in situ generation of a mixed metal hydroxide The thickening of usually aqueous clay suspensions with the aid of mixed metal oxides and mixed metal hydroxides is well-known prior art. By simply mixing together form due to electrostatic interactions between the clay component and the MMO / MMH adducts and network structures, creating a so called shear thinning rheology.
  • a disadvantage of these systems is the fact that they show due to their compositions a pronounced lability to ionic and in particular polyanionic impurities of the liquid phase.
  • residues of polyacrylates, lignosulfonates, lignites or polyanionic celluloses (PAC) in the mixing tank prevent the actually desired formation of rheology.
  • Another negative phenomenon is the leaching of lignosulphonates, humic acids, lignins and tannins from corresponding soil formations, resulting in loss of performance and rheology during the drilling process.
  • the object of the present invention was therefore to provide a new system with which the stabilization of the rheology of liquid phases based on a clay component a) and at least one mixed metal oxide (MMO) or mixed metal hydroxide (MMH) -containing component b) is possible.
  • MMO mixed metal oxide
  • MMH mixed metal hydroxide
  • the metal salt component used can be used preventively as well as subsequently for the regeneration of an already contaminated and damaged drilling fluid or drilling mud.
  • the present invention preferably also claims numerous variants with respect to such liquid phases.
  • the clay component a) should preferably be selected from the series of smectites, bentonites, montmorillonites, beidellite, hectorites, saponites, sauconites, vermiculites, illites, kaolinites, chlorites, attapulgites, sepiolites, palygorskites, halloysites and fuller's earths.
  • Clays of the smectite type and, in particular, hectorite are to be regarded as being particularly preferred, with montmorillonites and bentonites being particularly suitable.
  • the present invention provides a component b) which is thermally activated and preferably calcined hydrotalcites, hydrotalcite-like compounds or mixtures thereof.
  • the calcination should have taken place in the presence of sodium, with amounts of ⁇ 1000 ppm sodium and more preferably> 10,000 ppm sodium being preferred.
  • component b) may be calcined mixtures of individual components which are selected from the series MgO, Al 2 O 3 or one of its hydrates, Mg (OH) 2 or one of its hydrates, Na 2 (CO 3 J 2 or one of its hydrates, Ca (OH) 2 , Fe (OH) 2 or one of its hydrates, hydrotalcite, hydrotalcite-like compounds, or one of its hydrates and a cellulose component
  • a material is particularly preferred can be described by the following empirical formula according to WO 01/49406: M ' m M n (OH) (2m + 3n + q a + br) (A c ') a (B r ) b 'XH 2 O.
  • the calcination has been carried out particularly advantageous when the temperatures have been between 750 and 1500 0 C and preferably between 900 and 1000 0 C.
  • liquid phase in addition to the main components a) and b) additionally contains alumina and / or an organic nitrogen compound, with urea being preferred.
  • component b) may also be a mixed metal hydroxide compound corresponding to DE 199 33 176 A1 of the general formula M m D d T (OH) ( m + 2d + 3 + n ) (A n ) a - qH 2 O act.
  • thermally activated hydrated Mischmetallhydroxide to be regarded as particularly preferred, which can be described by the general formula [M 11 Lx M 111 X (OH) 2 ] (A n ) -x / n -qH 2 O.
  • the teaching of DE 199 33 176 A1 also constitutes a substantial part of the present disclosure.
  • coprecipitates which may also be present as component b) according to the invention in the liquid phase.
  • Another variant of the mixed metal hydroxides obtained by hydration as component b) are in situ generated Mischmetallhydroxide.
  • the starting compounds containing the respective components M “and M '" in salt or oxide form or mixtures thereof, such as Mg 11 OZNaAI 111 O 2 are present in the appropriate proportions and in the presence of a suitable base.
  • MMH generated in situ are known from EP 0 617 106 A1, which in this respect is a substantial part of this Revelation is.
  • liquid phases as described in US Pat. No. 6,906,010 are to be regarded as a substantial part of this disclosure since, as already stated, they are based on in situ generation of a mischmetal hydroxide, as is component b) of this invention.
  • the present invention also includes, as component b), compounds of the garnet type and in particular of the basic structure Ca 3 Al 2 (OH) I 2 .
  • Such MMH are sometimes referred to as Mischmetallsilikate, because the OH groups may be exchanged to a minor proportion of silicate residues.
  • Such compounds are known from WO 94/02556, the disclosure of which in this context is a substantial part of the present invention.
  • component b) and in particular the associated suitable variants illustrate the breadth of the possible composition of the liquid phase which is used according to the present invention together with the polyvalent metal salts.
  • the invention takes into account a preferred variant in which the polyvalent metal salts are used in proportions of from 0.1 to 10% by weight, based on the liquid phase. It has proved to be particularly advantageous if the metal salt component is used in proportions of from 0.5 to 2.5% by weight, based on the liquid phase.
  • polyvalent metal salts which are based on divalent or trivalent cations, which are selected in particular from the series Mg “, Ca”, Ba “, Cr””", Mn “"",Fe””", Co “"", Ni “"",Cu””", Zn “”", Al '", Ga'”and mixtures of corresponding metal salts, wherein the The present invention is not subject to restrictions with regard to possible counter anions. It should only be noted that there must be sufficient solubility of the salts in the underlying liquid phase.
  • CaCl 2 , MgCl 2 , AlCl 3 , CaSO 4 , MgSO 4 , Al 2 (SO 4 ) 3 , Al-acetate, Fe (NO 3 ) 3 and their hydrates and aqueous solutions of these salts are particularly preferred so-called brines.
  • the polyvalent metal salts used according to the invention comprise at least one polyvalent cation, in particular a polyvalent metal cation and at least one anion.
  • the polyvalent cation is in particular a divalent, trivalent, tetravalent or pentavalent cation, in particular a divalent or trivalent cation.
  • Preferred anions are halides, especially Cl “ , Br, J " or F ", and sulfate or nitrate.
  • liquid phase which contains at least the components a) and b), according to the invention, it may be water and / or oil-based systems, which may each be present in thickened form.
  • the present invention also takes into account a variant in which the liquid phase constitutes a drilling fluid which, in addition to the main components a) and b), may contain further additives, such as additional rheology control, filtrate reduction, density control, cooling and lubricate the drill bit and stabilize the borehole wall.
  • the present invention also includes a use variant in which the polyvalent metal salt component is added as a precaution to stabilize the rheology of corresponding liquid phases or is subsequently used for the purpose of regenerating an already contaminated liquid phase. In the latter case, it is advisable to add the metal salt component successively while controlling the rheological progress.
  • the hitherto existing disadvantages in MMO / MMH clay systems are clearly overcome, since the known lability to ionic and in particular polyanionic impurities in the liquid phase now no longer exists.
  • liquids contaminated with such impurities, and in particular drilling fluids can also be subsequently regenerated, thus stabilizing the rheology of the liquid phase.
  • the polyanions and the metal salt will neutralize each other to form charge-controlled interactions, thereby overcoming for the first time the prejudice that the presence of ions in drilling muds will only have a negative impact on their performance, and especially rheology.
  • polyvalent metal salts to stabilize the rheology of liquid phases based on a clay component a) and at least one mixed metal oxide (MMO) or mixed metal hydroxide (MMH) -containing component b).
  • MMO mixed metal oxide
  • MMH mixed metal hydroxide
  • component b which is mainly defined by empirical formulas, it may be thermally activated and especially calcined hydrotalcites.
  • special activated hydrated mixed metal compounds which have been obtained, for example, in situ by hydration. Also suitable are coprecipitates of mixed metal hydroxides.
  • the metal salt component which is used in proportions up to a maximum of 10 wt .-%, should preferably be a divalent salt, such as. As CaCl 2 or MgSO 4 .
  • a divalent salt such as. As CaCl 2 or MgSO 4 .
  • water and / or oil-based systems are optionally preferred in thickened form as the liquid phase, which may additionally comprise further functional additives.
  • the properties of the respective drilling muds based on an aqueous clay suspension were determined according to the regulations of the American Petroleum Institute (API), guideline RP13B-1.
  • API American Petroleum Institute
  • the rheologies were measured with a corresponding FANN viscometer at 600 and 300 revolutions per minute, from which the values for PV (plastic viscosity) and YP (yield point) are calculated.
  • the shear stresses were determined at 200, 100, 6 and 3 revolutions per minute.
  • the rheologies were measured before and after the addition of the contaminant, and after subsequent addition of a polyvalent metal salt.
  • Clarified is the subsequent stabilization of the rheology analogous to Example 1 using the formulation or mixing specification given therein, but deviating from this with 10.0 g lignite (Shallow Canadian Lignite) as a contaminant. Results: Table 2:
  • Example 3 shows the subsequent stabilization of the rheology analogously to Example 1 using the formulation or mixing instructions given there, but deviating from this with 2.0 g of PAC (polyanionic cellulose) as a contaminant.
  • PAC polyanionic cellulose
  • Example 4 shows the subsequent stabilization of the rheology analogously to Example 1 using the formulation or mixing instructions given there, but deviating from this with 5.0 g of MgSO 4 heptahydrate as stabilizing agent.
  • Example 5 shows the subsequent stabilization of the rheology analogous to Example 1 using the formulation given there or Mi see specification, but deviating from this with 5.0 g of iron (III) nitrate, Fe (NO 3 ) 3, as a stabilizing agent. Results: Table 5:
  • Clarified is the subsequent stabilization of the rheology analog
  • Example 7 shows the use according to the invention of polyvalent metal salts for stabilizing the rheology in the form of precautionary addition to a drilling fluid based on a clay suspension and a thickening MMO / MMH component. In the case of polyanionic contamination, this should prevent the known loss of viscosity.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne l'utilisation de sels métalliques polyvalents pour stabiliser la rhéologie de phases liquides à base d'un composant d'argile a) et d'au moins un composant b) contenant un oxyde métallique mixte (OMM) ou un hydroxyde métallique mixte (HMM). Concernant le composant d'argile a), des argiles de type smectites et notamment la bentonite sont préférées. Le composant b), défini principalement par des formules empiriques, peut être constitué d'un hydrotalcite activé thermiquement, et notamment calciné. Il est cependant également possible d'utiliser des composés métalliques mixtes hydratés activés spéciaux, obtenus par exemple in situ par hydratation. Les coprécipités d'hydroxydes métalliques mixtes conviennent également. Le composant de sel métallique, présent à hauteur maximale de 10 % en poids, est de préférence un sel divalent, tel que CaCl<SUB>2</SUB> ou MgSO<SUB>4</SUB>. Un système aqueux ou huileux, éventuellement sous forme épaissie, est préféré en tant que phase liquide, ledit système pouvant en outre comprendre des additifs fonctionnels supplémentaires.
PCT/EP2006/011193 2005-11-23 2006-11-22 Utilisation de sels metalliques polyvalents pour stabiliser la rheologie de phases liquides WO2007059941A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005055701.5 2005-11-23
DE200510055701 DE102005055701A1 (de) 2005-11-23 2005-11-23 Verwendung mehrwertiger Metallsalze zur Stabilisierung der Rheologie von Flüssigphasen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834372A (zh) * 2013-11-07 2014-06-04 北京中煤矿山工程有限公司 一种千米深矿井水平巷道围岩地面预注浆改性钻孔工作泥浆

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CN108070365B (zh) * 2017-12-14 2020-06-05 贵州省地质矿产勘查开发局一一五地质大队 一种适用于煤系地层钻进的水基钻井液及其制备方法
CN110954563B (zh) * 2019-12-10 2021-11-12 北京航空航天大学 一种用来原位观察半固态金属合金流变行为的装置与方法

Citations (3)

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WO1992018238A1 (fr) * 1991-04-16 1992-10-29 The Dow Chemical Company Produits d'addition a base d'argile et d'oxydes metalliques melanges actives
DE19933176A1 (de) * 1999-07-15 2001-01-18 Sueddeutsche Kalkstickstoff Verfahren zur Rheologiesteuerung von Flüssigphasen
WO2001049406A1 (fr) * 2000-01-06 2001-07-12 Edgar Franklin Hoy Compositions a rheologie modifiee et agents de modification

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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
US5343950A (en) * 1992-10-22 1994-09-06 Shell Oil Company Drilling and cementing extended reach boreholes
CA2115390C (fr) * 1993-03-22 1999-08-24 Bharat B. Patel Composition liquide constituee d'un aluminate metallique ou d'un promoteur de viscosite et d'un compose de magnesium, et methode d'utilisation de ladite composition
GB2378716B (en) * 2001-08-08 2004-01-14 Mi Llc Process fluid
US6906010B2 (en) * 2002-04-22 2005-06-14 Edgar Franklin Hoy Additives for preparing rheology-modified aqueous fluids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018238A1 (fr) * 1991-04-16 1992-10-29 The Dow Chemical Company Produits d'addition a base d'argile et d'oxydes metalliques melanges actives
DE19933176A1 (de) * 1999-07-15 2001-01-18 Sueddeutsche Kalkstickstoff Verfahren zur Rheologiesteuerung von Flüssigphasen
WO2001049406A1 (fr) * 2000-01-06 2001-07-12 Edgar Franklin Hoy Compositions a rheologie modifiee et agents de modification

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834372A (zh) * 2013-11-07 2014-06-04 北京中煤矿山工程有限公司 一种千米深矿井水平巷道围岩地面预注浆改性钻孔工作泥浆
CN103834372B (zh) * 2013-11-07 2016-07-06 北京中煤矿山工程有限公司 一种千米深矿井水平巷道围岩地面预注浆改性钻孔工作泥浆

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