WO1997034073A1 - Consolidation chimique, compatible avec l'eau et in situ du sable a l'aide de resine de furane - Google Patents

Consolidation chimique, compatible avec l'eau et in situ du sable a l'aide de resine de furane Download PDF

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Publication number
WO1997034073A1
WO1997034073A1 PCT/US1996/003559 US9603559W WO9734073A1 WO 1997034073 A1 WO1997034073 A1 WO 1997034073A1 US 9603559 W US9603559 W US 9603559W WO 9734073 A1 WO9734073 A1 WO 9734073A1
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WO
WIPO (PCT)
Prior art keywords
resin
water
formation
range
solution
Prior art date
Application number
PCT/US1996/003559
Other languages
English (en)
Inventor
Paul Shu
Original Assignee
Mobil Oil Corporation
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 Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to PCT/US1996/003559 priority Critical patent/WO1997034073A1/fr
Publication of WO1997034073A1 publication Critical patent/WO1997034073A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/02—Subsoil filtering
    • E21B43/025—Consolidation of loose sand or the like round the wells without excessively decreasing the permeability thereof
    • 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
    • C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
    • C09K8/57—Compositions based on water or polar solvents
    • C09K8/575—Compositions based on water or polar solvents containing organic compounds
    • C09K8/5751—Macromolecular compounds
    • C09K8/5755—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to the consolidation of
  • subterranean formations and, more particularly, to the water compatible in situ sand consolidation of subterranean formations with furan resin.
  • Furan resin has been used in situ chemical sand consolidation since the 1960's, as described in U.S.
  • Patents 3,199.590 and 3,209,826 Due to the reactivity of furan resin and it's incompatibility with water, early sand consolidation processes use a multi-slug injection,
  • furan resin is in the prepolymer stage of furfuryl alcohol (FA), as described by Grayson, ed. "Kirk- Othmer Encyclopedia of Chemical Technology,” 3rd edition, Vol. 11, pp. 499-527.
  • Furan resin available from Quaker Oat Chemicals is polymerized to a viscosity of 240-270 centipoise (at 55°C).
  • U.S. Patent 4,903,770 describes a furan based process for the sand consolidation in steam injected wells. It places a furfuryl alcohol/ester diluent/H 2 SO 4 mixture delivered with high quality steam after an ester-acid preflush to achieve a rapid consolidation near the
  • the resin To use furan resin, the resin must be deposited uniformly on the surfaces of sand grains. The water in the formation and the water that is a reaction product must be removed effectively for a strong bonding between resin and sand. Formation water removal by displacement with
  • the method of the present invention relates to water compatible chemical in situ sand consolidation with oil soluble furan resin.
  • the three step water compatible in situ chemical consolidation uses thermally and chemically stable furan resin.
  • the consolidation method of the present invention is based on the phase separation mechanism for the placement of the resin rather than conventional fluid displacement for better control of resin deposition and less consumption of chemicals.
  • the three component system of the present invention comprises furan resin, solvent and water.
  • the resin placement in the phase separation mechanism is controlled by the composition of the two phase system of resin-solvent and water and their mutual solubilities.
  • Resin phase separation takes place when the resin solution encounters water.
  • the method of the present invention results in high strength and high permeability
  • the method comprises the injection of resin/water miscible organic solvent solution followed by a spacer volume of water and acid catalyst injection.
  • the water compatibility and resin deposition are achieved by using water miscible organic solvents, such as alcohols, as the mutual solvent.
  • water miscible organic solvents such as alcohols
  • the resin solution flows through a water wet formation or reservoir it displaces the water.
  • the resin solution also deposits the resin on the surface of sand through mixing with water remaining in the pores. Surface water on the sand is removed by partitioning into the water miscible organic solvent phase. This method results in strong adhesion and bonding of the sand.
  • the invention therefore includes a sand consolidating method for an unconsolidated or loosely consolidated formation which comprises the steps of:
  • the method of the present invention involves a three step injection process to achieve a uniform and strong sand consolidation.
  • the method is water compatible and there is no need to dewater the formation prior to the resin
  • furan resin is injected as a solution in a water miscible organic solvent into a water- wet formation.
  • Water miscible organic solvents such as lower alcohols and acetic acid, are suitable delivery solvents for furan resin.
  • a uniform deposition of resin is achieved by it's phase separation from the water miscible organic solvent due to the introduction of water.
  • Resin deposition in the method of the present invention is less dependent on the formation permeability and the viscosity of subsequently injected fluid than in conventional fluid displacement methods.
  • Water in the formation is used advantageously to aid the deposition of the resin.
  • water in the pores is removed by partitioning into the water
  • miscible organic solvent phase which is moving forward to displace water in the pores. Thereafter, a spacer volume of water is directed into the well.
  • the mechanism can tolerate the wash by a large volume of water spacer over a range of flow rates.
  • the spacer volume of water does not wash out the resin due to the viscosity of the resin coating.
  • the spacer volume of water distributes the resin.
  • the spacer volume of water further extracts the water miscible organic solvent to concentrate the resin coating to
  • the spacer volume avoids plugging of the formation which would impede oil recovery, thereby obtaining a higher degree of permeability.
  • the aqueous acid further promotes the phase separation of the resin and extracts excess water miscible organic solvent from the deposited resin.
  • Phase-separated furan resin forms a plastic type material after curing with acid.
  • the amount of resin solution used to treat the formation is in the range of from 0.5 to 3 pore
  • Clean sand with a uniform size distribution requires less than about 1 pore volume of resin solution. Dirty, clay type sand with residual crude oil saturation, such as Berea sand, requires more than about 1 pore volume resin solution.
  • the resin solution comprises furan resin in an amount in the range of from 30 to 90 wt.%, and preferably in the range of from 40 to 80 wt.%, determined by the desired levels of resin deposition. Loose, weakly consolidated formation requires a high resin concentration to deposit a heavier resin coating on the sand grains. A tight
  • the resin solution further comprises solvent in an amount in the range of from 10 to 70 wt.%.
  • the solvents for use in the method of the present invention are water miscible organic solvents including water soluble
  • Carboxylic acids and alcohols of lower carbon numbers such as acetic acid, methanol and t-butyl alcohol, are preferred.
  • Methanol, acetic acid and t-butyl alcohol are especially useful because of the combination of excellent water miscibility and poor solvency for furan resin.
  • Furan resin precipitates from these solvents readily when water is introduced.
  • Hydrolyzable co-solvents may also be used in the resin solution in order to adjust the solvency and help the flow properties of the resin solution. Residual water which remains in the resin is believed to be eventually reduced by co-solvent hydrolysis, for example, by ethyl acetate hydrolysis and/or acetic anhydride hydrolysis, in the resin phase.
  • Co-solvents may be water miscible organic solvents and/or water immiscible organic solvents which can be converted to water miscible organic solvents upon
  • Co-solvents include anhydrides, such as acetic anhydride, and esters, such as methylorthoformate and ethyl acetate. Suitable combinations of solvent/co-solvent include acetic acid/acetic anhydride, alcohol/ester and acetic acid/ester. The amount of co-solvent is generally in the range of from 1 to 50 wt.%.
  • a preferred combination of solvent/co-solvent is acetic acid/acetic anhydride.
  • Furan resin precipitates from acetic acid solution rapidly and completely when water is introduced since it is a rather poor solvent for furan resin and has a high affinity to water.
  • Acetic anhydride is not miscible with water but gradually reacts with water to form acetic acid.
  • Acetic anhydride remains in the resin rich phase in the beginning of phase separation. It improves the mobility, or flow, of the resin phase and the distribution of resin.
  • Acetic anhydride also slows resin precipitation to prevent plugging. After the placement of resin, it gradually hydrolyzes to form water soluble acetic acid and diffuses into the water phase to leave a viscous resin coating on the sand surfaces.
  • a spacer volume of water, such as fresh water, is provided.
  • formation water, sea water and the like is directed into the well after placement of the resin.
  • pore volumes of spacer at a flow rate of 0.1 to 4 pore volumes per minute are used.
  • 4 to 10 pore volumes of spacer at a flow rate of 0.2 to 2 pore volumes per minute are used.
  • An acid catalyst solution is injected after placement of the resin and injection of a spacer volume of water.
  • a spacer volume of water Generally, at least about 1 pore volume of acid is required to set the resin. More generally, 2 to 8 pore volumes of acid is required to set the resin.
  • Suitable acids for use in the process of the present invention include strong mineral acids, such as HCl, H 2 SO 4 and H 3 PO 4 .
  • the acid strength is generally in the range of from 10 to 50 wt.%.
  • the resin is set and cured for a time period in the range of from 2 to 24 hours. Rapid setting of the resin is preferred to avoid resin leak-off from the target zone and shorten the well's down time.
  • the resin's setting rate is controlled by acid catalyst concentration and the formation temperature. For example, at a
  • a small amount, in the range of from 1 to 10 wt.%, of latent acid, such as triethylphosphate, can be added to the resin solution to improve acid-resin contact for a more complete curing of resin.
  • a silane coupling agent can also be added to the resin solution to promote coupling and adhesion of the furan resin to sand and other siliceous material in the
  • the silane coupling agent can be added in an amount in the range of from 0.1 to 5 wt.% and preferably in the range of from 0.2 to 2 wt.%.
  • a particularly suitable coupling agent is an amino silane compound or a mixture of amino silane compounds represented by the following formula:
  • R 1 is a straight, branched or cyclic chain alkyl radical having in the range of 1 to 8 carbon atoms
  • R 2 is hydrogen, an alkyl amine radical or an alkyl radical wherein the alkyl amine and alkyl radical have in the range of from 1 to 8 carbon atoms
  • R 3 is straight or branched chain alkyl radical having in the range of from 1 to 3 carbon atoms
  • n is an integer within the range of from zero to 10.
  • amino silanes are gamma- aminopropyltriethoxysilane, N-beta-(aminoethyl)-gamma- aminopropyltrimethoxysilane, N-beta-(aminoethyl)-N-beta- (aminoethyl)-gamma-aminopropyltrimethoxysilane, N-beta- (aminopropy)-N-beta-(aminobutyl)-gamma- aminopropyltriethoxysilane, and di-N-(beta-aminoethyl)- gamma-aminopropyltrimethoxysilane.
  • Preferred amino silanes are represented by the formula
  • R 4 is a straight or branched chain alkyl radical having in the range of from 1 to 4 carbon atoms
  • R 5 is hydrogen, an alkyl amine radical or an alkyl radical wherein the alkyl amine and alkyl radicals have in the range of from 1 to 4 carbon atoms
  • R 6 is an alkyl radical having in the range of from 1 to 2 carbon atoms
  • m is an integer in the range of from 1 to 4.
  • Examples of the above amino silanes are N- beta (aminoethyl)-gamma-aminopropyl-trimethoxysilane, N- beta-(aminoethyl)-N-beta-(aminoethyl)-gamma- aminopropyltrimethoxysilane and N-beta-(aminopropyl)-gamma- aminopropyltriethoxysilane.
  • the most preferred amino silane compound for use in accordance with the method of the present invention is N- beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane.
  • the process of the present invention uses resin placement by phase separation rather than conventional fluid displacement to provide better control of resin deposition.
  • Furan resin having the properties set forth below in Table 1, is used in the examples.
  • Sandpacks are treated with 1 PV, 20% HCl for 2-4 hours at room temperature to remove the carbonates in the sand. CO2 gas produced in an untreated sandpack interferes with the resin placement during HCl injection.
  • One inch diameter sandpacks are used.
  • the sandpacks are made up of 5g of 70-140 Granusil mesh sand packed at both inlet and outlet end, and 50 g of 310 mesh AGSCO sand in the middle.
  • One pore volume (PV) is equivalent to about 10-12 ml.
  • Fine 300 mesh nylon screens are used at the inlet and outlet ends of the sand pack.
  • Fluids are injected with a manual syringe.
  • the injection rates are calculated based on the volume and time of injection.
  • Examples 1-6 are summarized in Table 2 below. Examples
  • Example 1 and 2 show consolidation using t-butyl alcohol as the solvent.
  • Example 3 shows consolidation using acetic acid as the solvent.
  • Examples 4 and 5 show consolidation using acetic acid as the solvent with acetic anhydride as the co- solvent.
  • Example 6 uses acetic acid as the solvent and acetic anhydride as the co-solvent with a silane coupling agent.
  • the acid catalyst is between 20 -100 ml. (1.5-8 PV).
  • the water spacer injection rates vary between 0.6-20 ml./min (0.05- 1.7 PV/min.). It is preferred to inject the first 0.05-1 PV of water spacer at a lower rate.
  • the acid catalyst is
  • Examples 1-6 is in general inversely proportional to resin content in the unconsolidated sandpack.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

Cette invention concerne un procédé de consolidation chimique, compatible avec l'eau et in situ du sable, lequel procédé fait appel à de la résine de furane soluble dans l'huile. Cette consolidation in situ, chimique et compatible avec l'eau comprend trois étapes, et fait appel à une résine de furane stable sur les plans thermique et chimique. La mise en place de la résine se fait par séparation de phase plutôt que par le déplacement de fluide traditionnel. Ce procédé consiste à injecter une solution d'un solvant organique miscible dans la résine et l'eau, puis à injecter un volume d'eau séparateur et un catalyseur acide.
PCT/US1996/003559 1996-03-15 1996-03-15 Consolidation chimique, compatible avec l'eau et in situ du sable a l'aide de resine de furane WO1997034073A1 (fr)

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PCT/US1996/003559 WO1997034073A1 (fr) 1996-03-15 1996-03-15 Consolidation chimique, compatible avec l'eau et in situ du sable a l'aide de resine de furane

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PCT/US1996/003559 WO1997034073A1 (fr) 1996-03-15 1996-03-15 Consolidation chimique, compatible avec l'eau et in situ du sable a l'aide de resine de furane

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117229598A (zh) * 2023-11-10 2023-12-15 北京平储能源技术有限公司 二硫化钼纳米片Janus复合树脂及其制备方法与用途

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042032A (en) * 1973-06-07 1977-08-16 Halliburton Company Methods of consolidating incompetent subterranean formations using aqueous treating solutions
US4903770A (en) * 1988-09-01 1990-02-27 Texaco Inc. Sand consolidation methods
US5178218A (en) * 1991-06-19 1993-01-12 Oryx Energy Company Method of sand consolidation with resin
US5423381A (en) * 1993-10-29 1995-06-13 Texaco Inc. Quick-set formation treating methods

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042032A (en) * 1973-06-07 1977-08-16 Halliburton Company Methods of consolidating incompetent subterranean formations using aqueous treating solutions
US4903770A (en) * 1988-09-01 1990-02-27 Texaco Inc. Sand consolidation methods
US5178218A (en) * 1991-06-19 1993-01-12 Oryx Energy Company Method of sand consolidation with resin
US5423381A (en) * 1993-10-29 1995-06-13 Texaco Inc. Quick-set formation treating methods

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117229598A (zh) * 2023-11-10 2023-12-15 北京平储能源技术有限公司 二硫化钼纳米片Janus复合树脂及其制备方法与用途

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