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
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
  • C09K8/608—Polymer compositions
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/44—Preparation of metal salts or ammonium salts
• • 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
  • C09K17/00—Soil-conditioning materials or soil-stabilising materials
  • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
  • C09K17/18—Prepolymers; Macromolecular compounds
  • C09K17/20—Vinyl polymers

Definitions

• This invention relates to a method for stabilizing clay formations by injection into the formation of a cationic compound.
• the underground reservoirs of fossil hydrocarbons often consist of clay rocks. During the drilling and operation of these reservoirs, the clay comes into contact with water foreign to the deposit. However, contact with water has a detrimental effect on the stability and permeability of clayey rocks.
• the reservoir loses its permeability and its stability.
• the production of hydrocarbons is disturbed and the mechanical characteristics of the rock can be lowered.
• US Patent 3,382,924 suggests the use of polymers or inorganic complexes.
• US Patent 4,366,074 relates to the use of homopolymers formed from a monomer containing a cationic site.
• European patent 92,340 relates to the use of cationic polymers used in improved recovery operations.
• the cationic polymer according to the invention is an ammonium salt, quaternary of the product of the reaction of a polyamine containing at least one unsubstituted amino group with a copolymer formed from units derived:
• R 1 is a C 1 -C 3 alkyl radical
• the copolymer contains 1 to 4 moles of units deriving from the ethylenically unsaturated monomer per unit deriving from the unsaturated alpha-beta-dicarboxylic compound and preferably 1 to 2 moles.
• the unsaturated alpha-beta-dicarboxylic compounds used in the composition of the copolymer are more particularly maleic acid or anhydride or alkylmaleic acids, for example methylmaleic or citraconic acid.
• ethylenically unsaturated monomers are vinyl aromatic compounds such as vinyltoluene, styrene and alphamethylstyrene, olefins, such as ethylene, propylene, isobutene, butene, pentene, heptene, l octene, nonene, decene, dodecene, and vinyl ethers such as methylvinyl ether and isobutylvmyl ether.
• vinyl aromatic compounds such as vinyltoluene, styrene and alphamethylstyrene
• olefins such as ethylene, propylene, isobutene, butene, pentene, heptene, l octene, nonene, decene, dodecene
• vinyl ethers such as methylvinyl ether and isobutylvmyl ether.
• the polyamines used must have a primary amine group, to allow the formation of a five-membered imide ring with the two neighboring carboxyl groups of the copolymer and at least one other tertiary amine group which can be quaternized.
• the pclyamines used are of general formula
• Z represents an alkylene or cycloalkylene radical.
• This radical can carry substituents, such as hydroxyl groups or preferably tertiary amines.
• R 3 and R 4 which are identical or different, represent a hydrocarbyl radical, preferably C 1 to C 12 alkyl and preferably C 1 to C 4 alkyl.
• polyamines As an example of these polyamines, mention may be made of dimetylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylammopropylamine, methylpropylaminoaraylamine and propylbutylaminoethylamine.
• an alkyl halide or a C 1 to C 12 and preferably C 1 to C 4 dialkyl sulfate is used; mention may be made of methyl bromide, iodide, chloride or sulphate or ethyl sulphate.
• the preparation of the cationic compound according to the invention comprises three stages: the copolymerization, the reaction with the polyamine and finally the quaternization.
• the copolymer can be prepared by conventional methods of radical polymerization.
• the preferred method is solution polymerization in the presence of a radical initiator.
• radical initiators peroxides or peroxydicarbonates are generally used.
• the solvent must be compatible with the initiator used.
• aromatic solvents such as cumene, p-cymene, xylene, toluene, or else hydrocarbon cuts of aromatic nature.
• Ketones such as for example methyl ethyl ketone are also suitable.
• the copolymerization reaction is carried out by continuous or discontinuous addition of the radical initiator to the solution of the comonomers, at a temperature between about 30 and 300 ° C.
• the copolymerization time depends on the nature of the monomers and initiators used. In general it is between 2 and 6 hours.
• the polymer is redissolved in a solvent for the polymer and the polyamine used. Generally it is an aromatic solvent. The same solvent is usually used as for the copolymerization.
• the polyamine is added either all at once at the start of the reaction or gradually during the reaction.
• the proportion molar corresponds substantially to the proportion of alpha-beta-dicarboxylic compound involved in the preparation of the copolymer. This proportion can be for example from 0.9 to 1.1 mole of polyamine per alpha-beta-dicarboxylic compound.
• the reaction temperature can vary widely, it is generally between 100 and 300 ° C and preferably between 100 and 200 ° C. At these temperatures the water of the reaction is continuously removed.
• the duration of the reaction is generally between 1 and 10 hours, a duration of the order of 3 hours being generally sufficient.
• the formation of the imide function is verified by IR spectroscopy, by the disappearance of the bands of the anhydride function at 1780 cm and 1855 cm -1 and the appearance of the bands of the imide function at 1700 cm -1 and 1770 cm -1.
• the quaternization reaction can be carried out according to known methods. It is advisable to use the same solvents as above, so it is not necessary to isolate the imide from the copolymer prepared in the previous step.
• the quaternization takes place with a satisfactory speed even at room temperature, we are content to cool the previous solution before the introduction of the alkyl halide or dialkyl sulfate. At room temperature the reaction time can vary from a few minutes to a few hours depending on the ratio of the two constituents. In general, 0.5 to 1.5 moles of quaternization reagent are used per mole of polyamine.
• the quaternization is carried out with an efficiency of 30 to 100% and often from 50 to 100% depending on the operating conditions (measured by NMR).
• the quaternized copolymer precipitates as it is formed. It is recovered by filtration.
• solutions of these cationic copolymers are injected into the formation. In general, this treatment takes place before the formation comes into contact with foreign water. However, it is possible to repeat the stabilization operation several times by injecting new solutions.
• the solvents used are generally alcohols or mixtures of solvents based on alcohols.
• aqueous solutions are used.
• the concentration of these solutions, as well as the volume and the flow rate of the injected liquid are determined according to the characteristics of the formation.
• solutions are used whose concentration varies between 0.1 and 10% by weight and preferably between 0.5 and 5%.
• the effectiveness of the copolymers in stabilizing clays is evaluated by comparison of the permeability of the rocks, before and after treatment with a solution of copolymer.
• This parameter translates the reactivity of the fine fraction and the degree of reversibility of the phenomena to which it is subjected (essentially swelling and dispersion of the clays).
• the reactor is maintained at a temperature of 80 ° C for 4 hours.
• the product is filtered and then dried.
• the reference water is permuted water.
• the copolymers are in aqueous solution.
• the fluids used are deaerated with nitrogen and filtered at 0.22 ⁇ m to avoid the incidence of corrosion and clogging phenomena on the course of the experiments.
• a bactericide allows, if necessary, to get rid of bacterial developments.
• Tables 1 and 2 summarize the results of drainage tests with sandstone from the Vosges and sandstone from the Gulf of Guinea.
• MICAS + CLAYS 16% Clays are for 1/3 of the chlorites and for 2/3 of the illites. All are diagenetically recent and therefore very sensitive to the phenomena studied.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Soil Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Applications Claiming Priority (2)

Publications (1)

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• 1986
  • 1986-12-17 FR FR8617672A patent/FR2608622A1/fr not_active Withdrawn
• 1987
  • 1987-12-15 EP EP88900380A patent/EP0298096A1/de not_active Withdrawn
  • 1987-12-15 WO PCT/FR1987/000502 patent/WO1988004680A1/fr not_active Application Discontinuation
  • 1987-12-16 GR GR871916A patent/GR871916B/el unknown
  • 1987-12-17 ES ES8703611A patent/ES2005482A6/es not_active Expired
• 1988
  • 1988-08-15 SU SU884356304A patent/SU1755709A3/ru active
  • 1988-08-17 OA OA59410A patent/OA08750A/xx unknown

Non-Patent Citations (1)

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