Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
• • 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
  • C09K8/035—Organic additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

Definitions

• Zwitterionic polymers comprising betaine-type units and use of zwitterionic polymers in drilling fluids
• the present invention relates to new polymers comprising betaine type units, as well as the use of zwitterionic polymers in drilling fluids, in particular as an agent for inhibiting swelling of clays.
• drilling fluids are used intended to lubricate, clean and cool the drilling tools and the drilling head , and / or to evacuate the material released during drilling (cleared rocks). Drilling fluids are also used to clean the well. They also provide the pressure necessary to support the wall of the well before consolidation. The fluids are usually called “drilling muds”. After drilling, the well walls are generally consolidated with a cementitious material. During drilling, the walls of the rock, in particular clayey rocks sensitive to water, tend to swell. Operational problems are linked to these clays. The swelling can hinder the flow of fluid or the passage of the drilling tool.
• the swelling can lead to a disintegration of the wall. This disintegration can cause irregularities in the well and thus create points of mechanical weakness.
• the disaggregated clay material is released into the fluid and can cause problems in controlling the viscosity of the fluid: clay materials, with or without the presence of a high concentration of salts (brine), tend to increase strongly viscosity. This increase can be harmful: if it becomes too large, the drilling tools are damaged. The well can even be made unusable.
• the clayey rocks excavated can have a tendency to aggregate in the drilling fluid. We are talking about an accretion phenomenon. Accretion can hinder the circulation of fluids, and can mechanically block the drilling head (“bit-balling” phenomenon).
• PHPA partially hydrolyzed polyacrylamide
• HTHP high temperature high pressure
• Another object of the invention is to provide a polymer which can be used as an agent for inhibiting swelling of clays and / or as a filtrate reducing agent and / or as a lubricating agent and / or a 2- in-1 for the lubrication and inhibition of swelling of clays, for example in drilling fluids, in particular in aqueous or non-aqueous fluids, in particular in fluids based on silicates.
• the invention further provides alternatives to polymers comprising acrylamide units.
• the invention provides a zwitterionic polymer, comprising units comprising a betaine group, characterized in that it comprises: - at least 35 mol% of units comprising a betaine group, the betaine group comprising a cationic group and a group anionic, and - additional units chosen from: - alkoxylated units of the following formula: -CH 2 -CHR 6 [-X 2 - (CH 2 -CH 2 -O) n -R 7 ] - in which: - R 6 is an atom of hydrogen or a methyl group, - X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H 4 -CH 2 - - n is a whole or average number greater than or equal to 1 , - R 7 is a hydrogen atom, an alkyl group or a tristyrylphenyl group, and / or - the hydroxylated units of the following formula: -CH 2 -
• the invention also relates to a drilling fluid, and more particularly to a well drilling fluid for oil and / or gas, comprising the polymer.
• the fluid may in particular be a fluid based on silicates.
• the invention also relates to the use of a zwitterionic polymer comprising at least 35 mol% of units comprising a betaine group, the betaine group comprising a cationic group and an anionic group, in a drilling fluid, as clay swelling inhibitor, and / or as accretion inhibitor, and / or as a fluid rheology control agent, and / or as a filtrate reducer and / or as a lubricating agent, for example as a agent for consolidating the walls of a well or for inhibiting the accretion of cleared drilled rocks (inhibition of "bit-balling" phenomena) or lubrication, or as a 2-in-1 agent, for lubrication and consolidation of well walls or inhibition of accretion, or for inhibition of swelling of clays (or
• the polymer can also be used as a filtrate reducer.
• Polymer The polymer according to the invention comprises at least two types of units. It is therefore a copolymer.
• the polymer is preferably a random copolymer. according to a preferred embodiment, the polymer does not comprise other units than those mentioned.
• the polymer preferably has only the units comprising a betaine group and the alkoxylated units, or only the units comprising a betaine group and the hydroxylated units.
• the polymer is therefore preferably a binary copolymer, as opposed to a terpolymer.
• molar mass when we speak of molar mass, it will be the average molar mass in absolute mass, expressed in g / mol. This can be determined by aqueous gel permeation chromatography (GPC), by light scattering (DDL or even MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide ...) according to the polymer composition.
• GPC gel permeation chromatography
• DDL or even MALLS light scattering
• an aqueous eluent or an organic eluent for example dimethylacetamide, dimethylformamide
• a unit derived from an acrylic or methacrylic acid ester does not cover a unit of formula -CH 2 -CH (COOH) -, -CH 2 -C (CH 3 ) (COOH) -, - CH 2 -CH (OH) -, respectively, obtained for example by polymerizing an ester of acrylic or methacrylic acid, or vinyl acetate, respectively, then by hydrolyzing.
• the polymer comprises units comprising a betaine group comprising a cationic group and an anionic group. Within these units, the number of positive charges is equal to the number of negative charges. The units are electrically neutral. These units are zwitterionic units, the polymer is therefore zwitterionic. The polymer is thus generally electrically neutral, insofar as the other units are neutral. This is the case for the polyalkoxylated units or the hydroxylated units present in the polymer. The proportion in moles of units comprising a betaine group is at least 35%.
• the betaine group has a permanent anionic charge and a permanent cationic charge in at least one pH range.
• the polymer according to the invention can also be obtained in a known manner by chemical modification of a polymer known as a precursor polymer.
• sulfobetaine units can be obtained by chemical modification, using a sultone (propanesultone, butanesultone), a haloalkylsulfonate or any other sulfonated electrophilic compound, a polymer with pendant amino functions.
• R 6 is a hydrogen atom or a methyl group
• X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H -CH 2 -
• - n is a whole or average number greater than or equal to 1
• - R 7 is a hydrogen atom, alkyl group, or a trystyrylphenyl group.
• the monomer is such that: - n is greater than or equal to 10, and - R 7 is an alkyl group comprising from 12 to 30 carbon atoms, preferably from 18 to 25.
• the Sipomer BEM sold by Rhodia
• n is equal to approximately 25
• the number of carbon atoms is 22.
• the monomer is such that: - n is greater than or equal to 10, and - R 7 is a tristyrylphenyl group.
• An example of an alkoxylated monomer for this third embodiment is cited Sipomer SEM 25, sold by Rhodia, in which n is equal to approximately 25.
• the monomer is such that: - n is greater than or equal to 10, and - R 7 is a hydrogen atom.
• the polymer according to the invention can also comprise hydroxylated units of the following formula: -CH 2 -CHR 6 [-X 2 -R 8 ] - in which: - R 6 is a hydrogen atom or a methyl group, - X 2 is a group of formula -CO-O-, -CO-NH - or -C 6 H -CH 2 - - R 8 is a hydrocarbon group with at least two carbon atoms, comprising at least two -OH groups, preferably on two consecutive carbon atoms.
• the hydroxylated units can also be obtained by chemical modification of a precursor polymer containing, for example, epoxy units:
• Drilling fluids The invention relates, in one aspect, to a drilling fluid comprising the polymer. It can be an aqueous or non-aqueous fluid. It can be an aqueous fluid, based on silicates (or "silicate-based mud"), or without silicates. It can be an aqueous fluid, based on phosphates, or without phosphates. These can be fluids without phosphates or silicates.
• the polymer content in the drilling fluid is advantageously between 0.1% and 10%, preferably between 0.1% and 5, and even more preferably between
• aqueous fluids based on silicates or the uses in these fluids, the polymers comprising the hydroxylated units are particularly advantageous.
• polymers comprising alkoxylated units are particularly advantageous.
• the drilling operations consist in digging a hole by means of a tungsten carbide drill bit in particular, fixed to hollow rods screwed end to end.
• mud or drilling fluid, comprising additives in a liquid carrier, is injected into the drill string.
• This mud then rises through the borehole, outside the rods, and entrains elements of rocks detached during the drilling operation.
• the mud charged with the rocks establishes a back pressure which consolidates the hole.
• the mud is then extracted from the borehole to be rid of the rocks it contains before being injected again into the hollow drill rods. Under such processing conditions, additives added to the sludge give it a particular rheological behavior.
• Drilling fluids are known to those skilled in the art. The exact composition of the fluid may depend on the destination of the fluid. It may depend in particular on the temperatures and pressures to which the fluid will be subjected, on the nature of the rocks crossed by the well, and on the nature of the drilling equipment. Drilling fluids generally comprise a liquid vector and additives dissolved or dispersed in the liquid vector.
• Liquid sodium or potassium silicates are solutions of water-soluble glasses of the chemical formula: M 2 O ⁇ (SiO 2 ), where M can be Na + or K + and n is the molar ratio (the number of molecules SiO 2 for a molecule
• the latter are more expensive than sludge with water, but may be preferred in the case of drilling very deep wells (HP / HT drilling conditions; high pressure high temperatures).
• the polymer can be used with both types of vectors. However, water-based vectors (water mud) are preferred, in particular silicate-based vectors (silicate-based mud).
• the polymer according to the invention can enter into the composition of the drilling fluid in replacement or in addition of a well bore consolidation agent and / or filtrate reducing agents and / or agents lubrication, and / or accretion inhibiting agents.
• a well bore consolidation agent and / or filtrate reducing agents and / or agents lubrication, and / or accretion inhibiting agents are examples of the additives which may be included in the drilling fluids, in addition to the wall consolidation agents and / or the filtrate reducing agents, there are:
• - rheology control agents these can be agents making the viscoelastic fluid, rheofluidifiers, thickening agents. Mention is made, for example, of polysaccharides, such as guar or starch, xanthan gums, and derivatives of these compounds.
• - dispersants for example polymers comprising units derived from acrylic acid or vinyl sulfonic acid.
• agents for controlling the density of the fluid for example Barium sulfate.
• salts such as chlorides for example.
• mineral salts to promote the precipitation of certain ions, if they are present, and in particular divalent ions.
• Mention may be made, for example, of the addition of sodium carbonate to precipitate calcium, or sodium bicarbonate to precipitate lime, in particular during reforings in cement.
• Mention may also be made of the addition of gypsum or calcium chloride to limit the swelling of clays, the addition of calcium hydroxide, or slaked lime, to debicarbonate sludges contaminated with carbon dioxide.
• the drilling fluid according to the present invention can comprise usual additives from the class of high molecular weight polysaccharides, such as succinoglycan, wellan, gellan, useful as viscosants.
• Other conventional additives for applications relating to the exploitation of petroleum deposits can enter into the composition of the fluid.
• free radical transfer agents such as lower alcohols, thioureas, hydroquinone; biocides, chelating agents, surfactants, defoamers, anti-corrosion agents for example.
• Matter disaggregated consists of fine platelets which can alter the rheological properties of the fluid, and thus impede its circulation, and / or block the drilling tool.
• An agent for inhibiting the swelling of clays aims to prevent the penetration of the fluid into the rocks along the walls, to inhibit swelling and / or disintegration. It may be a consolidation of the well walls ("well bore consolidation"). Cleared clay rocks, particularly clay shales, suspended in fluids, can be problematic. These suspended rocks can swell, disintegrate, and thus modify the rheological properties of fluids, as explained above.
• An agent for inhibiting the swelling of clays aims to prevent penetration into the cleared rocks in suspension, and / or to inhibit disintegration.
• Accretion inhibiting agent On the other hand, suspended rocks tend to aggregate. We are talking about accretion. The aggregates formed can hinder the circulation of the fluid and the tools. They can also come to wrap the drilling head and thus block it (phenomenon of "bit-balling" in English). An agent for inhibiting the accretion of excavated drilled rocks aims to avoid these phenomena. It is noted that a common agent can form a film, or be adsorbed, on the surface of cleared rocks without preventing their agglomeration (accretion). A poorly suited clay swelling inhibitor may even promote this accretion. There is a need for agents combining the inhibition of clay swelling and the inhibition of accretion.
• Reducing filtrates Reducing the filtrate is the avoidance of loss of fluid in the well by. infiltration into rocks. Loss of fluid should be avoided for economic reasons (cost of the fluid), for safety reasons, and for productivity reasons. In fact, if the fluid fails, the drilling tools can be damaged due to overheating, poor lubrication, or mechanical blockage by poorly evacuated rocks and necessitate a temporary stop of the operation of drilling.
• the polymers according to the invention also exhibit interesting rheological properties (increase in viscosity) in the presence of high salt concentrations (brines).
• the polymers can in particular be used as agents 2 in 1, or more, combining several functions chosen from the following - inhibition of swelling of the clays and / or consolidation of the walls of a well ("well-bore consolidation"),
• the polymer which comprises the hydroxylated units is advantageously used.
• the drilling fluid is preferably a fluid for drilling a well intended for the recovery of oil and / or gas.
• the polymer content in the drilling fluid is advantageously between 0.1% and 10%, preferably between 0.1% and 5, and even more preferably between 1% and 3%.
• the polymer is an agent for inhibiting swelling of clays. It can thus be a consolidation agent for the walls of the well. It can thus be, also or alternatively, an agent for inhibiting the accretion of cleared drilled rocks.
• the polymer may also or alternatively be a reducing agent for filtrates.
• Example 4 HomoPolvmere comprising SPE units (03VTA149, "SPE")
• Example 5 Polymer comprising SPE units and vicinal diol units (03VTA021, "SPE / GMMA 99.9 / 0.1"):
• the reaction medium is maintained at 80 ° C for 6 h.
• the heating is then stopped.
• the final product is an aqueous solution characterized by a dry extract of 42.8% (calculated by weighing a known quantity of solution before drying and after drying at 115 ° C for 2 h). This solution is too viscous for its pH and Brookfield viscosity to be measured under the same conditions as for the polymers described in the examples above.
• Example 7 HomoPolvmere comprising SHPP units (04CVG031, "SHPP"):
• the monomer (SHPP) is synthesized and then polymerized, the final polymer being characterized by a weight-average molar mass of 200,000 g / mole (relative value).
• CHPSNa sodium chlorohydroxypropylsulfonate, sold by the company Raschig
• CHPSNa sodium chlorohydroxypropylsulfonate
• the pH of this solution is then adjusted to 7.5 using 10% sodium hydroxide solution.
• 47.72 g of dimethylaminopropylmethacrylamide, sold by the company Rohm, or 0.280 moles, are introduced. The mixture is heated to 80 ° C. and maintained at this temperature for 4 hours.
• solution I The aqueous solution thus obtained (solution I) is characterized by a dry extract of 24.7% (calculated by weighing a known quantity of solution before drying and after drying at 115 ° C for 2 h) and a pH of 8.7 .
• 1 H NMR analysis in D20 shows that the transformation of the tertiary amino monomer into sulfobetaine monomer is almost complete: 93% of dimethylaminopropylmethacrylamide is transformed into SHPP monomer.
• 36.67 g of this solution I and 137.5 g of water are charged at ambient temperature in a 1.5 L double-jacketed SVL reactor equipped with a teflon anchor and connected to a thermostat. The mixture is heated to 85 ° C. When this temperature is reached (time noted t °), are introduced: - continuously for 2h (from t ° to t ° + 2h) using a syringe pump: 330g of solution I
• Example 8 Fluid comprising a polymer
• a formulation B of silicate-based drilling mud is prepared comprising the following ingredients
• Silicates (Silicates 60N20, Rhodia 5% (dry matter)
• Clay particles are used to simulate the cuttings.
• the clay used is Oxford clay
• Extrusion test Hot rolling is carried out in the presence of the clay particles, at 65 ° C. for 16 hours, as indicated above. After, the particles are collected on a sieve, washed with brine and extruded in a CT 15 Compressometer device from ADAMEL LHOMARGY, at a speed of 40 mm / min. The pressure necessary to extrude the particles is measured. It is dependent on the degree of hydration of the particles. The harder the particles, the higher the pressure, the better the protection against water penetration, and therefore the better the clay swelling inhibiting effect.

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