DE2425312C3 - Method for the treatment of non-load-bearing, underground formations - Google Patents

Description

NH ₂ - R ₁

NR ₁

in which: Ri is a straight-chain, branched-chain or cyclic alkyl radical with 1 to 8 carbon atoms, R _{2 is} hydrogen, an alkylamine radical or an alkyl radical with 1 to 8 carbon atoms, R3 is a straight-chain or branched-chain alkyl radical with 1

45 Si (OR ₃ J ₃

(D

to 3 carbon atoms and η is an integer from 0 to 10.

8. The method according to claim 7, characterized in that the aminosilane has the general formula

NH ₂ - R ₄ - \ - NR ₄ Si (OR ₆ J ₃

(H)

in which: R4 is a straight-chain or branched-chain alkyl radical having 1 to 4 carbon atoms, R5 is hydrogen, an alkylamine radical or an alkyl radical having 1 to 4 carbon atoms, R _{6 is} an alkyl radical having 1 to 2 carbon atoms and m is an integer from 1 to 4.

The invention relates to a method for the treatment of non-bearing, underground, of one »Hole drilled through formation to prevent sand particles from being transported out of the formation into the > ear hole during the pumping of fluids from the irmation, using liquid, water-based Compositions of at least one curable, organic resin with an aminosilane and / or an aliphatic amine having about 6 to 20 carbon atoms in the aliphatic chain, wherein the liquid composition mixed with an aqueous carrier liquid and the mixture in the Formation to form a permeable packing between the subterranean formation and the

do drill hole introduced and hardened there will.

Such formations, unless special precautions are taken, often become loose Particles washed out with the fluid and into the

ns borehole produced where the particles hit the pumping equipment Abrasion, filter or suction baskets dirty and the effective production surface of the borehole can decrease.

One method of controlling the formation of particulates from a non-structural subterranean formation penetrated by a borehole involves mixing particulate! Material comprising a dispersion of a curable composition i of organic resin in liquid hydrocarbon to form a slurry of resin coated particles. The resin-coated particles are brought into contact with the subterranean formation to form a permeable packing ι o between the subterranean formation and the borehole. The resin coated particles are held in contact with the formation until the resin has hardened.

Another way of controlling the formation of particles from a non-structural, subterranean formation penetrated by a borehole includes the use of a Dispersion of a curable composition of organic resin in liquid hydrocarbon. The resin composition has an affinity for the particles in the subterranean formation and coats the particles of the formation as the dispersion is forced through the subterranean formation. The Resin is cured to form a hard resin matrix to strengthen the subterranean formation.

There are many developments in the procedures for treating a borehole penetrated, underground formation. Flushing solutions were developed to prevent the formation to prepare the intake of the treatment fluids, furthermore chemical additives were developed, To treat clay contained in the formation, hardeners have also been developed to raise the resin Curing strengths, coupling agents and surfactants have also been developed to address the Bond between the resin and the particles used to pack the formation or the Particles in the subterranean formation were used to improve.

Many of the treatment modalities control the promotion of particles from a non-load bearing, from A borehole penetrated subterranean formation include the use of a liquid Hydrocarbon to bring the liquid resin composition into contact with the subterranean formation bring. Liquid hydrocarbons are expensive, however, and a significant proportion of those from chemicals incurred costs occurred in the treatment of non-load-bearing, subterranean formations. With so the increasing value of liquid hydrocarbons and increasing demands for liquid Hydrocarbons, so that there are now supply difficulties with liquid hydrocarbons, it is therefore desirable to find a substitute for the liquid hydrocarbon used in methods is used to treat a subterranean formation penetrated by a borehole, around herein the promotion of particles ims the Control formation. ho

From US Pat. No. 2,378,817 there is one working method known for the consolidation of underground formations, a solution of a phenol-formaldehyde resin is used with an anti-wetting agent. However, this is a (> s "Single-phase solution", in addition, it is stated that the particles of the formation were previously dried and possibly Water should be removed. There is therefore nothing in this document about the use of an aqueous one Phase-containing solidifying liquid stated. From US Patent 36 25 287 is that The use of a resin in aqueous solution is known, but this document does not mention anything about it stated that a solid material should be treated with it first and then such a slurry of the resin-coated solid material is introduced into the borehole to consolidate the formation will. Furthermore, from US patent specification 32 08 525 the use of a mixture of solid particles, z. B. sand, and a resin known, this mixture is introduced from above into a borehole, however, an impermeable plug should be formed in the borehole with the help of the mixture, to separate formations in a fluid-tight manner. Such a plug should not contain liquids let pass, while the object of the invention is to achieve a solidification that is porous, i.e. liquid permeable. In US Pat. No. 3,587,742, the use of an epoxy resin is with Amine hardeners and various types of wetting agents described, but this is a Resin dissolution system, d. H. also no slurry of solid particles with a curable Resin coated.

It has now been found that a liquid resin composition which is a curable organic resin and an aminosilane, an aliphatic amine with about 6 contains up to 20 carbon atoms in the aliphatic chain or mixtures thereof, in an aqueous Carrier liquid can be dispersed, and that the liquid resin composition has an affinity for silica (Silicon dioxide), so that the liquid resin composition has a resin coating on silica forms when the dispersion is brought into contact with silica. Such a resin composition forms a coating on the silica which is non-sticky and which leads to a high resin Strength can be cured. A slurry of such resin-coated silica particles can be displaced through a conduit without the particles coming together to form a Glue compound that could clog the line.

The inventive method is therefore characterized in that a liquid composition of previously described type is dispersed in the aqueous carrier liquid that this dispersion initially with a particulate material is mixed into a slurry, the particulate Material is coated with the liquid composition that the slurry is then in the underground Formation is introduced and that the particulate material coated with the composition maintained in contact with the subterranean formation until the resin has hardened.

In an advantageous embodiment, the resin is an epoxy resin, phenol aldehyde resin, furfuryl alcohol resin, Urea aldehyde resin or a mixture thereof is used. Advantageously, about 0.5 to 10 parts by weight of the liquid resin composition · per 100 parts by weight of the aqueous carrier liquid dispersed in the aqueous carrier liquid, the liquid resin composition being the curable, organic resin and about 0.1 to 10 parts by weight of the aminosilane and / or the aliphatic amine, which Has 8 to 18 carbon atoms in the aliphatic chain, for 100 parts by weight of resin.

In an advantageous embodiment, phenol-formaldehyde resin is used as the phenol-aldehyde resin and as Urea aldehyde resin Urea formaldehyde resin used, the viscosity of the liquid resin composition is about 5 to 20,000 cP at 26.7 ° C.

Advantageously, the liquid resin composition is applied to a viscosity of about 10 to 500 cP 26.7 ° C set, the liquid resin composition in addition to the curable, organic resin about 0.5 to 5 parts by weight of the aminosilane and / or des aliphatic amine per 100 parts by weight of the curable organic resin

In a further advantageous embodiment, the liquid resin composition additionally comprises a diluent for the curable organic resin, the particulate material being sand.

Advantageous aminosilanes are represented by the following general formula:

Si (OR ₃ J ₃ (1)

NH ₂ -R ₁ - ^ - N - R ₁

whereinRi is a straight-chain, branched-chain or cyclic alkyl radical with about 1 to 8 carbon atoms, R _{2 is} hydrogen, an alkylamine radical or an alkyl radical in which the alkylamine or the alkyl cst have about 1 to 8 carbon atoms, R _{3 is} a straight-chain or branched-chain alkyl radical with 1 to 3 carbon atoms and π is an integer from 0 to 10.

Aminosilanes encompassed by the general formula (1) given above are, for. B.

gamma- aminopropyltriethoxysilane,

N-beta- (aminoethyl) -gamma-aminopropyltri-

methoxysilane,

N-beta- (aminoethyl) -N-beta- (aminoethyl) -

gamma-aminopropyltrimethoxy-silane,

N-beta- (aminopropyl) -N-beta- (aminobutyl) -

gamma-aminopropyltriethoxysilane and

Di-N- (beta-aminoethyl) -gamma-aminoprcpy!

trimethoxysilane.

The preferred aminosilanes are represented by the following general formula:

₃ (2)

wherein: R4 is a straight or branched-chain alkyl radical with 1 to 4 carbon atoms, R5 is hydrogen, an alkylamine radical or an alkyl radical in which the alkylamine or alkyl radical has about 1 to 4 carbon atoms, R _{6 is} an alkyl radical with 1 to 2 carbon atoms and m is an integer from 1 to 4.

Aminosilane encompassed by general formula (2) are / .. B.

N-beta- (Aminoalliyl) -gamma-aminopropyltri-

melhoxysilane,

N-bcta- (aminoethyl) -N-beta- (aminoethyl) -

gamma-aminopropyltrimethoxysilane and

N-bctii- (aminopropyl) -

p.imma-aniinopropyltriiilhoxysilane.

Useful aliphatic amines are aliphatic ^ · Amines having from about 6 to 20, and preferably from about 8 to 18 carbon atoms in the aliphatic chain. Examples such beneficial amines are:

Octylamine, coconut oil lamb, soybean oil amine,

Tallowamine, oleylamine, caprylamine,

n-Tetradecy! amine, palmitylamine,

Octadecylamine, stearylamine, laurylamine acetate,
ίο palmitylamine acetate, stearylamine acetate,

primary amine acetate, which is derived from

Coconut fatty acids,

primary amine acetate, which is derived from

Sebum fatty acids,
primary amine acetate which from

Is derived from soybean fatty acids,

Soy trimethylammonium chloride,

Dicoconut dimethylammonium chloride.

Tallow trimethylammonium chloride,
Lauryltrimethylammonium chloride,

Palmityltrimethylammonium chloride,

Steary'trimethylammonium chloride,

Coconut trimethylammonium chloride,

the reaction product of soybean oil amine
and5 moles of ethylene oxide and

the reaction product of n-octadecylamine

with 5 moles of ethylene oxide.

Usable curable organic resins are liquid at 27 ° C and they are made by heating the resin or cured by bringing the resin into contact with a hardener. Examples of commercially available Usable resins are epoxy resins, phenol aldehyde resins, furfuryl alcohol resins and urea aldehyde resins. These resins are available in various viscosities depending on the molecular weight of the Resin and the concentration of the diluent mixed with the resin depend. The usage of resins or resin-diluent mixtures having a viscosity at 27 ° C of about 5 to 20,000 centipoise (cP) are preferred. Most preferred resins and resin-diluent mixtures have viscosities of about 10 at 27 ° C up to 500 cP. The preferred resins are epoxy resins, phenol-formaldehyde resins, urea-formaldehyde resins and furfuryl alcohol resins.

Hardeners for the liquid organic resins can be incorporated into the resin composition, or the resin composition can be brought into contact with a hardener after the resin is in Contact has been made with the non-load-bearing, subterranean formation. In the resin composition entered hardeners are selected so that the resin composition is cured after the resin composition was brought into contact with the non-structural subterranean formation is. Hardeners incorporated in the resin composition should further be selected so that the hardener has limited solubility in the aqueous wedge of liquid carrier.

Suitable hardeners for epoxy resin compositions can, although this is not a limitation, amine hardeners such as

fts Dimethylaniinopropylamin, Bcnzyldimeihylamin,

Diethylaminopropylamine, diethyltriainine,
Metaxylenediamine, metaphenylenediamine.
Diaminoilipheny! Methane. Piperidine,

Tridimethylaminomethylphenol,
acidic anhydride hardeners such as
Oxalic anhydride, phthalic anhydride.
Pyromellitic dianhydride.
Dodecinyl succinic anhydride,
Hexahydrophthalic anhydride and
Methylbicyclo- (2.2, l) -5-hcpteni-2,3-dicarboxylic acid anhydride and
Polymercaptan hardener

include.

Suitable hardeners for inclusion in furfuryl alcohol, phenol aldehyde and urea aldehyde resin compositions can, but this is not a limitation, hexachloroacetone. 1,1,3-trichloro rifluoroacetone, Benzotrichloride. Include benzyl chloride and benzal chloride.

Suitable hardeners for dispensing furfuryl alcohol, phenol aldehyde and urine aldehyde resin compositions by bringing these resin compositions into contact with the hardener, wherein however, this is not a limitation in terms of ayl halide compounds such as phthaloyl, fumaryl and benzoyl chloride, halogenated, organic acids and acidic acids Chemicals like trichloroacetic acid, hexachloroacetone. Benzotrichloride, acetic acid and formic acid as well as inorganic acids such as hydrochloric acid.

Useful aqueous fluids are aqueous fluids which do not contain contaminants which clog the non-structural subterranean formation to be treated. Surface water, lake water, and water produced from underground formations have all been found to be useful. The pH of the aqueous carrier liquid is essential. The acid in an aqueous liquid, which has a low pH, can degrade the performance of the amino compounds, thereby requiring the use of higher concentrations of amino compounds than. they would otherwise be required in neutral or basic, aqueous liquids .

Furthermore, it was found that surfactants can be entered into the liquid resin composition or mixed with the aqueous liquid in order to increase the strength of the cured resin and to prevent the resin becomes sticky, so that the resin coated particles do not stick together. Cationic surfactants are considered non-emulsifying. surfactants are known and they may be incorporated into the carrier fluid or the resin composition to prevent the dispersion of the resin composition dispersed in the carrier from being converted into an emulsion. The concentration of surfactant is essential. A low concentration of surfactant is advantageous and the benefits generally increase with concentration. However, a high concentration of surfactant can be detrimental. However, the useful concentration of surfactant can be determined by experiment. Useful cationic surfactants are commercially available in the form of many product names.

Diluents for controlling the viscosity of the curable organic resin have also been found to be advantageous. The amount of urine on the silicate surface can be controlled in part by the viscosity of the liquid resin composition. The surface area covered per volume of the resin, the resulting permeability of a matrix coated with resin and the strength of the matrix coated with resin are functions of the thickness of the resin coating. Reactive diluents are often used to control the viscosity of resin compositions, which are used to control the

ίο Extraction of particles from non-load-bearing, underground Formations used are preferred.

It is also advantageous to use a diluent with limited solubility in the carrier fluid to select. The carrier liquid competes with the resin for the diluent, and it can play a part of the diluent from the resin composition dispersed therein. By setting the Concentration of the partially soluble diluents and the partially soluble components of the resin can be the viscosity of the liquid resin composition. which is dispersed in the aqueous liquid, being controlled. The viscosity of the resin component partly determines the surface area of the resin can coat, and the permeability of the

2s resin coated matrix.

Suitable diluents for epoxy resins can, without this signifying a restriction, Styrene oxide, octylene oxide, furfuryl alcohol, phenols, furfural, liquid, from the reaction of EpichlorhyCrin and Monoepoxides derived from monohydroxyl compounds such as allyl glycidyl ether, butyl glycidyl ether and Phenylglycidyl ether and liquid diepoxides, e.g. B. the diglydicyl ether of resorcinol include.

Suitable diluents for furfuryl alcohol

ts resins. Phenol aldehyde resins and urea aldehyde resins without this being intended to be a restriction. Furfuryl alcohol, furfural. Phenol and cresol.

Other treatment chemicals for non-pregnant, underground formations are also useful.

Pre-washes to condition the non-structural formation and chemicals to affect clay are examples of such useful treatment chemicals. Sized particles for attaching a permeable packing in contact with a non-structural subterranean formation which have an affinity for aminosilanes are also useful. To form a permeable packing, a sand with a mesh size of 0.42 to 0.25 mm is usually used. The resulting packing has sufficient permeability or permeability so that it does not obstruct the flow of the fluids conveyed through it and only inhibits the movement of particles of the formation through it

ss Other components can be in the aqueous Carrier liquid or added to the liquid resin composition. A surfactant Agent can be added to the aqueous liquid to convert the dispersion to a To prevent emulsion. In the aqueous carrier liquid or in the resin composition can Chemicals to control tone are entered. The viscosity of the resin composition can vary with Thinners can be adjusted. Boundary surface -active agents can be added to the resin, to improve the bond between the resin and the subterranean formation. However, this is not a complete one

709 621/281

List of components, which if necessary or preferably the aqueous liquid carrier wedge or can be added to the liquid resin mixture.

The invention is explained in more detail with reference to the following examples.

Example I.

It became a furluryl alcohol resin with surfactants Agents, diluents and various aminosilanes have been studied to determine the influence of these Components to be determined on a dispersion of furfuryl alcohol resin in an aqueous carrier liquid. The furfuryl alcohol resin had a viscosity at 25 "C" in the range of about 240 to 440 cP, a specific gravity in the range of about 1.205 to 1.220, one pH in the range of about 4 to 4.8 and an average molecular weight of about 225,121 g this resin became homogeneous with the concentrations of given in Table 1 below Aminosilanes, diluents and surfactants mixed together. 5.5 g of these resin mixtures were then mixed with 0.66 g of Htxachloraceton as hardener for the resin. This mixture was then used in 400 ml of an aqueous carrier liquid dispersed, which fresh water mixed with 5 parts by weight of sodium chloride to 100 parts by weight of water. 48 g of white sand with a mesh size of 0.42 to 0.25 mm was mixed with the dispersion, and

Table I.

Influence of aminosilane, diluent and surfactant on coating and strength

this mixture was stirred for a period of 3 (minutes while heating the mixture with konstantei speed of 22.2 "C at 40.6 ⁰ C Dei sand was then examined to determine whether there;.. resin had coated the sand mil Han Coated sand was then packed into a 22.3 mm inner diameter glass tube to a height of 88.9 mm, and the aqueous carrier fluid was flushed through the pack to simulate the loss of carrier fluid in a formation where the sample became cured for 2 hours in a bath at 60 ° C. The samples were then cooled to 26.7 ° C. and compressive strength measurements were carried out.

The values in Table 1 show that furfuryl alcohol resin mixed with aminosilanes in a aqueous carrier liquid came to be dispersed and that the resulting resin composition a Has affinity for silica (quartz) so that the resin composition has a resin coating on Kie Silica surface forms when the resin is brought into contact with silica (quartz).

These values also show that one with a mixture of furfuryl alcohol resin and an aminosi lan-coated sand pack can be cured to a matrix with high strength and that quickly surfactant to the resin mixture to improve the compressive strength of a Har Coated sand packing can be added.

Furfural

(G)

Surfactant, agent

(6)

Viewing ability

NH2 (CHj) iSi (OC.'H;) j: 113 0.95 113 0.95 none 0.95 none 0.95

Compressive strength
after 24 h at 60 ⁰ C tung Aushfr
(kp / cm ² at
26.7 ⁰ C)

NH: (CH2) 2NH (CHj) 3Si (OCHj) s:

0.95 11 3

0.95 113

0.95 none

0.95 none

NHXCH _ ') 2NH (CH2): NH (CH2) jSi (OCH3) ₃ :

0.95 113

0.95 113

0.95 none

0.95 none

No silane:

None

None

None

None

113
113
none
none

0.96 none 0.96 none

0.96 none 0.96 none

0.96 none 0.96 none

0.96 none 0.96 none none
none
Well
none

Well
Well
Well
Well

Well
Well
Well
Well

small amount
none
none
none

none
none
108.6
none

85.8
58.5
182.5
168.9

97.4
77.0
276.2
182.3

> 7.0
none
none
none

*) The surface-active agent is a commercially available mixture of quaiernary amines and diluents.

Example2

A resin composition consisting of 121 g of the furfuryl alcohol resin used in Example 1, 113 g of furfural and the surfactant concentration listed in Table II below was mixed with the one in the table
specified silane to - Determination of the influence of:

¹ T

of Table II on the ability of the furfuryl alcohol resin to coat silica particles mixed. This series of tests was carried out using the procedure described in Example 1 except that the aqueous carrier fluid was fresh water and not a hardener with the resin had been mixed.

The values in Table 11 show the coating properties of a resin blend containing aminosilanes contains. Resins which contain aminosilanes having at least two amino groups are good ones Coating properties, while an aminosilane with only one amino group has the coating ability of a resin promotes when it is added to the resin composition in a high concentration. Silanes which contain no amino groups have no effect on the ability of the resin to Coating of silica particles, if not in combination with a cationic surfactant Funds are used. Cationic surfactants improve the ability of a silane containing resin composition for coating silica particles.

Table Il

Influence of different silanes on the coating Table II (continued)

Silane
(G)

Surface active agent ")

Capable of pulling over

CHiSi (OCHi) ₁ : 0.95 1.21 none 1.21 none 8.47 CH ₃ Si (OOHi) ₃ : 0.95 1.21 none 1.21 none 8.47 C ₅ HnSi (OCiHs) ₃ : 0.95 1.21 none 1.21 none 8.47 CoHiSi (OOHs) ₃ : 0.95 1.21 none 1.21 none 8.47 02HsSi (OQHs) ₃ : 0.95 1.21 none 1.21 none 8.47

C2H3Si (CHsCO2) 3:

1.21 0.95

1.21 none

8.47 none

HS (CH2) aSi (OCH3) 3:
Ul 0.95

UI none

8.47 none

Well

none

none

gu;

none

none

Well

none

none

Well

none

none

Well

none

none

Well

none

none

Well

none

none

Silane

Border capability wedge for surface coating
active

Medium')

I Ί
O - CH ₂ - CHCH ₂ O (CH ₂ ) ₃ Si (OCH 3) 3 1.21
1.21
8.47 0.95
none
none gul
none
none ^ V (CH ₂ J ₂ Si (OCH ₃ ),
0— ', ) 1.21
1.21
8.47 0.95
none
none Well
none
none CH ₂ CCH ₃ CO ₂ (CH ₂ J ₃ Si (OCH; ,) ₃ 1.21
1.21
8.47 0.95
none
none small amount
none
none NH ₂ (CH ₂ I ₂ Si (OC ₂ H ₅ J ₃ 1.21
1.21
8.47 0.95
none
none excellent
small amount
Well NH ₂ (CH ₂ I ₂ NH (CH ₂ J ₃ Si (OCH, ,) 3 1.21
1.21
8.47 0.95
none
none excellent
excellent
excellent

NH ₂ (CH ₂ J ₂ NH (CH ₂ I ₂ NH (CH ₂ J ₃ Si (OCH ₃ J ₃

1.21 0.95 excellent

1.21 none excellent

8.47 none excellent

*) At de.i! surfactants are eir commercial mixture of quaternary amines and diluents.

At game 3

The compressive strength of a with Furfurylalkoholhar; coated sand pack which tongues have been manufactured by the method described in Step Example 1 operation wai and comparable Furfurylalkoholharzzusammenset containing the silanes listed in the following Table II were measured. Be the aqueous carrier fluid in this example is it is fresh water containing 0.25 part by weight of a commercially available mixture of quaternärei amines and diluents to 100 parts by weight of water The resin composition was eii mixture which g 035 in the Table II indicated silanes, 121 g of the furfuryl alcohol resin which was used in Example 1, 113 g of furfural to 0.96 g of a commercially available, surface-active Mil means in the form of a mixture of quaternary amines and diluents

The values in Table III show that silanes without Amino groups only resin-coated sand packs

genes form low strength and that the strength of a resin-coated sand pack with the The number of amino groups in the silane structure increases.

Table III

Influence of different silanes on strength

At sp! e 14

CH ₃ Si (OCH ₁ ),

CH ₁ Si (OC ₂ H ₅ ),

C ₅ G ₁₁ Si (OC ₂ H ₅ ),

CH ₅ Si (OC ₂ H ₅ ).,

C ₂ H ₁ Si (OC ₂ H ₅ J ₃

C ₂ H ₃ Si (OCH ₃ CO ₂ J ₃

Cl (CH ₂ I ₁ Si (OCH _{3 I 3}

HS (CH ₂ J ₃ Si (OCH ₃ J ₃

O - CH ₂ - CHCH ₂ O (CH ₂ I ₃ Si (OCH ₁ J ₃

NH ₂ (CH ₂ J ₃ Si (OC ₂ H ₅ J ₃
NH ₂ (CH ₂ J ₂ NH (CH ₂ J ₃ Si (OCH ₃ J ₁ NH ₂ (CII ₂ J ₂ NH (CH ₂ J ₂ NH (CH ₂ J ₃ Si (OCH ₃ )., 77.0

Druckfcsiigkcii after curing for 24 h at 60 C (kp / cm ² at 26.7 ¹ Cl

<7.0

<7.0

■ - · 7.0 <7, () <7.0 <7.0 <7.0 <7.0

<7.0 - 7.0

41.5 58.5 The solubility of a resin composition dispersed in an aqueous carrier solution is determined at various temperatures. In this series of tests, the resin composition was obtained by mixing 49.5 parts by volume of the furfuryl alcohol resin used in Example 1 with 49.5 parts by volume of furfural, 0.5 parts by volume of N-beta- (aminoethyl) -gammaaminopropyltrimethoxysilane and 0 , 5 parts by volume of a commercial mixture of quaternary amines and diluents per 100 parts by volume of the resin composition. The aqueous carrier solution was fresh water in which 8 parts by volume of sodium chloride, 0.5 part by weight of calcium chloride, 0.2 part by weight of magnesium chloride and 0.25 part by volume of a commercial mixture of quaternary amines and diluents per 100 Parts by volume of fresh water were dissolved.

The values of the following Table IV / pertain to the partial solubility of the dispersing in the salt solution I resin compositions. It can be seen that the Solubility of the resin composition in the salt solution is not proportional to the concentration of that in the Resin compositions dispersed in salt solution increases, and that greater than about 20 parts by weight of the resin composition dispersed in the aqueous carrier liquid are required to maintain the viscosity of the resin composition. Hence wire the viscosity of the resin composition is low reduced as the concentration of the resin dispersed in the saline solution is increased. the These values also show that the aqueous carrier liquid is partially present in the liquid resin composition. is soluble and that the volume of the resin compositions! tongue by the aqueous carrier liquid, which is ir of the liquid resin composition dissolves, can be increased.

Table IV

Viscosity and distribution of resin in an aqueous phase

Resin mixture, Temperature of Parts by volume of resin per Viscosity of the Parts by volume of resin Fluids 100 parts in the salt Resin, which mixture per 100 solution dissolved not in the Parts of resin salt Resin mixture Saline solution on mixed solution solved CQ (cP) 5 40.6 10 40.6 faO > 1000 20th 40.6 27 32 30th 40.6 - (12) enters the 37 Resin one 5 60.0 10 60.0 57 > 1000 20th 60.0 22nd 40 30th 60.0 20th 46 5 933 10 933 52 813 20th 933 23 58 30th 933 20th 4OJ Example5

The compressive strength and the permeability of a sand pack which had been consolidated by means of the resin used in Example 4 and heated to 93.3 ° C. were determined after the resin composition had been dispersed in the saline solution, this being 20 parts by weight and 30 parts by weight Parts by weight shark

per 100 parts by weight of the resin-salt solution mixture contained, it was heated to 3.3 ° C. and the solubilities were determined according to the procedure described in Example 4. The dispersions were flushed through a pack of saline-wetted sand to build up the resin on the sand pack. The sand packing was a packing of white sand with a mesh size of 0.21 to 0.089 mm, which was piled up in a glass tube with an inner diameter of 22.3 mm to a height of 88.9 mm. The resin was removed by flushing of 200 cc of a 7.5% aqueous solution of Sahsäure in fresh water heated to 93.3 ⁰ C, cured by the sand pack. The solution used to cure the resin composition contained 0.1% of an acid inhibitor to reduce the acid's ability to corrode the metal components of the test system. The solidified sand pack was cured for 16 hours at 933 ° C. and then cooled to room temperature to measure the permeability and strengths.

The values in Table V below show that a resin composition dispersed in an aqueous carrier liquid by a sand pack to consolidate this sand pack into a permeable one Matrix can be flushed through. In this investigation, the strength of the consolidated matrix and the permeability of the consolidated matrix by increasing the concentration of those in the aqueous Carrier liquid dispersed resin composition increases.

Table V

Strength and permeability of a sand pack which is dispersed with in saline solution Resin has solidified

Resin (parts by weight
100 parts by weight of the
Resin saline mixture)

Compressive strength after curing for 16 seconds at 93.3 ^t: C

(kp / cm? at 26.7 ⁰ C) Permeability (Darcies)

upper part

lower part

20th
30th

lOO.b
114.8

3.35
4, b

2.6
3.15

Example6

The ability of epoxy and phenol-formaldehyde resin compositions to coat silica particles and the strength of a package of the resin coated particles were determined. This series of tests was carried out according to the procedure described in Example 1. The phenol-formaldehyde resin had a viscosity at 37.8 ⁰ C of about 1,000 cP and a pH of about 6.8. The epoxy resin had a viscosity at 26.7 ⁰ C from about 100 to 16OcP and contained no diluent. The hardener for the epoxy resin was a commercial polymercaptan hardener. The hardener for the phenol-formaldehyde resin was hexacetone. The diluent for the epoxy and phenol formaldehyde resin is furfural. For both resins, the silane was N-Bcta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.

The values in Table VI below show that the epoxy resin compositions i'nd the phenol formal

dehyde resin compositions can be dispersed in aqueous carrier fluids and that these resin compositions dispersed in the aqueous carrier fluids have an affinity for silica surfaces, so that they form coatings on the silica surfaces. These data also show that epoxy and phenol-formaldehyde resin compositions containing aminosilanes having at least two amino groups form coatings on sand particles so that a package of the resin-coated sand particles has high strengths after ¹ cure.

Table Vl

Influence of diluent, silane and surfactant on the coating and strength of

Epoxy and phenolic hydrochloride resins

resin Harder 16 Dilution Silane Interfaces capability Compressive strength Ib medium active agent *) to be after 24 h 16 layers Harden at 79 ° C (kp / cm ² at (G) (G) (G) (G) (G) 26.7 ° C) Epoxy: 116.4 120 113 0.95 0.9b Well 52.7 116.4 120 113 none 0.96 Well 7.0 116.4 none 113 none none Well none 116.4 none none none none none none Phenol-formaldehyde resin ·. 121 113 0.95 0.96 Well 160.8 121 113 0.95 none Well 3b2.7 121 113 none none Well 7.0

-UiicliemiktiVc means is a semi-permanent mixture of quaicrnärcn amines and diluents.

A ⁰

17 '1

B e i s ρ i e 17

A furfuryl alcohol resin composition. Which 121 g of furfuryl alcohol resin, as used in Example 1, 0.95 g of N-beta- (aminoethyl) -garr.maaminopropyltrimethoxysilane, 0.96 g of the surfactants shown in Table VH and 113 g Furfural was used for testing with various surfactants. at This study was 5.5 g of the resin composition with 0.66 g of hexachloroacetone as a hardener for the Resin mixed. The resin composition was dispersed in 400 ml of a 5% sodium chloride solution. 48 g of white sand with a particle size of 042 to 0.25 mm was mixed with the dispersion to obtain the To layer resin on the sand particles. The sand particles were then packed in a glass tube, and the Strengths were determined according to the procedure described in Example 1

The values in Table VI below show that surfactants are incorporated into the resin composition can be entered to increase the strength of the resin-coated sand pack. This Data also show that additional surfactant is added to the carrier fluid can decrease the strength of a resin-coated sandpack.

Table VII

Influence of surfactants on strength a resin-coated sand pack

Added. Additional. none Results of the interfaces
active agent ¹ border area
^; ) active agent. 1 Compressive strength
at 26.7 ° C added to 24 h hardening the carrier fluid at 60 ⁰ C (ecm) (kp / cm ² ) None none 57.1 Anionic medium 3N none 79.9 1 19.5 Cationic medium 5N none 85.8 1 43.8 9N none 57.7 I. 43.0 ION none 25.6 I. 29.2 11N none 87.7 1 21.9 12N none 72.1 1 15.8 13N none 89.1 I. 73.3 14N none 57.1 I. not hardened I5N none 67.9 1 <7.0 16N none 92.9 I. 30.0 Myristyldi none 53.0 methyl-benzyl- I not hardened animoniuni- chloride 17N 86.4 one resin coated not the sand

Those with the abbreviations N, surface-active Agents are commercially available mixtures of surfactants.

B e i s ρ i e i 8

Various concentrations of a cationic surfactant have been made into resin compositions added, which contained aminosilanes, in order to reduce the influence of the concentration of surfactants Agents on the ability of the resin composition dispersed in an aqueous carrier liquid to determine the overlaying of silica particles. The ability.?. " for coating silica particles is determined by measuring the strength of a packing of these particles according to that described in Example 1 Working method established. The resin composition is made by mixing 121 g of furfuryl alcohol resin, as used in Example 1 with 113 g of furfural and 0.95 g of the silane shown in Table VIII. 5.5 g of the resin composition then at the surfactant concentration! shown in Table VIII and 0.66 g

Table VIII

Hexachloroacetone as a hardener for the resin composition mixed. This mixture is then dispersed in 400 ml of a 5% sodium chloride solution. 48 g of white sand with a mixing width of 0.42 to 0.25 mm are then mixed with the dispersion Layering the resin on the sand mixed. The coated sand is then packed in a glass tube, and the compressive strengths are determined according to the procedure described in Example 1.

The values in Table VIII show that cationic, Surfactants increase the resulting strength of a resin-coated sand pack be able. However, concentration is critical and high surfactant concentrations are required decreases the strength of a pack of resin-coated sand particles.

Influence of surfactant concentration on the strength of a package of resin coated silica particles

Silane

NH2 (CH3) 3Si (OC2H5) 3:

2NH (CH2) 3Si (OCH3) 3:

NH2 (CH2) 2NH (CH2) 2NH (CH2) 3Si (OCHs) j:

The resin does not coat the sand.

The resin coated the sand initially, but some of this became apparent during the agitation period

washed away.

5N Compressive strength at 26.7 ° C after one Hardening for 24 hours at 60 ° C (G) (kp / cm *) 0.0275 none ¹ ) 0.055 none') 0.110 none ¹ ) 0.2035 none ² ) 0.220 79.9 0.275 31.6 0 58.5 0.0275 82.5 0.055 85.8 0.165 95.7 0.275 53.0 0.550 35.4 0 77.0 0.0275 101.8 0.055 98.1

B e i s ρ i e 19

A furfuryl alcohol resin composition containing 121 g of the furfuryl alcohol resin used in Example 1, 0.95 g N-beta- (aminoethyl) -gamma-aminopropyltritnethoxysilane, 113 g of furfural and 0.96 g of the surfactant 5N containing was dissolved in aqueous Solutions shown in Table IX below, and the ability of the resin to Overdraft determined. This coating test was carried out according to the procedure described in Example 1.

The values in Table IX show that one is a curable organic resin and an aminosilane containing resin composition in many aqueous

do media can be dispersed while doing their Maintains affinity of silica surfaces, so that the resin composition adheres to the silica surface coats when the dispersion is brought into contact with the silica surface. These values

f, _{5 also} show that aqueous, acid-containing liquids can have an adverse effect on the ability of the resin dispersed in the aqueous liquid to coat silica surfaces.

Table IX

Influence of various constituents on the ability of the resin to coat silica surfaces

Aqueous solution

Ability of the resin to coat sand

Fresh water good

Fresh water + 2% KCl good

Fresh water + 5% NaCl good

Fresh water + 15% NaCl good

Fresh water + 2% CaCb good

Fresh water + 10% CaCb good

Fresh water + 20% CaCb good

Standard saline solution ¹ ) good

Sea salt solution ² ) good

Fresh water + traces of NaOH good

Fresh water + traces of KOH good

Fresh water 4- sodium bicarbonate well

Fresh water + guanidine carbonate good

Fresh water + 2% HCl none

Fresh water + 2% acetic acid none

Fresh water + 2% citric acid none

Fresh water + 2% maleic acid none

Fresh water + 2% oxalic acid none

') Standard salt solution consists of water, NaCl, CaCb and MgCb ■ 6 H2O, in respective weight ratios of 240: 18.1: 1.34: 1 are mixed together.

² ) This sea salt solution consists of 41.95 g sea salt dissolved in enough fresh water to make 1 liter of solution. The sea salt is a mixture of 58.49 parts by weight of NaCl, 26.46 parts by weight of MgCl: 6 H2O, 9.75 parts by weight of Na2SO4, 2.765 parts by weight of CaCb, 1.645 parts by weight of KCI, 0.477 part by weight NaHCOi, 0.238 part by weight KBr, 0.071 part by weight H3BO3, 0.095 part by weight SrCb · b H2O and 0.007 part by weight NaF for 100 parts by weight sea salt.

Example 1 O

A curable, organic resin is dispersed in an aqueous carrier liquid, which various. Amino group-containing compounds contains, to the influence of these amino groups contained border Compounds on the ability of the curable, organic resin to coat gravel surfaces ascertain. These studies were carried out by adding about 1 g of the amino groups

containing compound mixed with 75 g of fresh water, about 3 ecm of that used in Example 1 Furfuryl alcohol resin dispersed in the aqueous mixture and about 10 g of sand with a mesh size from 0.42 to 0.25 mm into the aqueous dispersion

were interfered. The mixture was stirred for about 45 seconds and the resin allowed the ability to Coating of the sand was noted

There were those listed below. Amino groups containing compounds according to the above

investigated the procedure described, and the resin dispersed in the aqueous mixture on the sand piled up:

Octylamine, oleylamine, decylamine,
Coconut oil amine, dimethyl coconut oil amine,

Palmitylamine, tallowamine, dimethylstearylaniine,

Siearylamine, soybean amine, laurylamine.

sec. hydrogenated sebum amine,

Methyl sec soybean oil amine,
Dicoconut dimethylammonium chloride,

dihydrogenated tallow dimethylammonium chloride.

the reaction product of coconut oil amine

with 5 moles of ethylene oxide,

the reaction product of soybean oil amine
with 15 moles of ethylene oxide,

the reaction product of tallow amine

with 2 moles of ethylene oxide,

Caprylylamine acetate, palmitylamine acetate,

Stearylamine acetate, taigamine acetate and
Soybean oil citrate.

Claims (7)

Patent claims: 1. Method of treating a non-structural subterranean hole intersected by a borehole Formation to prevent the transport of sand particles from the formation into the borehole during the production of fluids from the formation, using liquid, hydrous Compositions of at least one curable, organic resin with an aminosilane and / or an aliphatic amine with about 6 to 20 carbon atoms in the aliphatic chain, wherein the liquid composition mixed with an aqueous carrier liquid and the Mix in the formation to form a permeable packing between the underground Formation and the borehole is introduced and caused to harden there, characterized in that that the liquid composition is dispersed in the aqueous carrier liquid, that this dispersion initially with a particulate material is mixed into a slurry, the particulate material is coated with the liquid composition that the slurry is then transferred to the underground Formation is introduced and that the particulate coated with the composition Material is maintained in contact with the subterranean formation until the resin has hardened. 2. The method according to claim 1, characterized in that the resin is an epoxy resin, Phtnolaldehydharz, Furfuryl alcohol resin, urea aldehyde resin or a mixture thereof is used. 3. Method according to one of the preceding Claims characterized in that about 0.5 to 10 parts by weight of the liquid resin composition to 100 parts by weight of the aqueous carrier liquid in the aqueous Tiigerflü ^ .Tkeit be dispersed, where Jie liquid riar / zui = rr> composition the curable, organic March and about 0.1 to 10 parts by weight of A.ninosiSans and / or the aliphatic amine, which has 8 to 18 carbon atoms in the aliphatic chain, contains resin per 100 parts by weight. 4. The method according to claim 3, characterized in that that phenol formaldehyde resin as phenol aldehyde resin and urea formaldehyde resin as urea aldehyde resin may be used, the viscosity of the liquid resin composition being about 5 to 20,000 cP at 26.7 ° C. 5. The method according to claim 4, characterized in that the liquid resin composition a viscosity of about 10 to 500 cP at 26.7 ° C is set, the liquid resin composition in addition to the curable, organic resin, about 0.5 to 5 parts by weight of the aminosilar and / or the aliphatic amine per 100 parts by weight of the curable organic resin. 6. The method according to claim 5, characterized in that the liquid resin composition additionally comprises a diluent for the curable organic resin and the particulate Matei iai is sand. 7. The method according to any one of the preceding claims, characterized in that the aminosilane the general formula