Water-compatible epoxide-phenyl backfill compound

FIELD: chemistry.

SUBSTANCE: compound is a set of expoxide-containing resin containing a resinous part and amine-type curing agent. The epoxide resinous base is obtained through epoxidation of an aromatically conjugated hydroxyphenylene, having degree of polycondensation n=2, obtained at temperature 240-260°C from diphenol (alkyl resorcinol), with diglycidyl ether of diethylene glycol with degree of polycondensation n=0-2 in molar ratio 1:5, respectively; epoxidation is carried out at temperature 120-165°C in the presence of 0.15-0.35 wt % 2,4,6-trisdimethylaminomethylphenol to weight ratio of epoxide groups of 6.0-9.0% and the resinous part further contains 15-25 wt % process water and the following content of ingredients of the compound, pts.wt: said resinous part 100, amine-type curing agent 2.0-12.0.

EFFECT: high efficiency of sealing water influx.

2 cl, 1 tbl

 

1. Scope

To date, the task of effective plugging water shut-off when oil is not resolved as evidenced by the fact that in most cases the oil is transported in containers and tanks with contaminated water content of up to 30-70 wt.%.

The invention relates to polymeric materials, in particular epoxy compounds "cold" curing, thermosetting amine hardeners in the presence of water and dissolved mineral salts.

The compound is suitable for curing in the right horizon of the soil with the formation of the solid is not soluble in water, but swelling of the polymer, for example, with the elimination of water from the perforated intervals annular space in the extracted oil and gas drilling oil and gas wells or for fixing soils Sesotho space trunks salt mines and drifts. The compound can be used for sealing joints and damage in various designs under the ground, such as sewers, basements, as well as in the transfer of liquid waste (including radioactive waste), located in the lower part of the bottoms of ships and vessels, in solid or gel with fixing them, and subsequent mechanical removal of the danger zone for recycling.

2. The level of technology

there are many polymeric compounds and compositions used to eliminate water production during drilling for oil and gas, capable of forming gels or solid materials.

Counterparts, close to the proposed solution technical solution containing the composition of their songs epoxy compounds.

The composition containing alkylresorcinol resin with hardener amine type (A.S. USSR №486129, EV 33/138, bull. No. 36, 1975), however, in this solution, the compound has a high viscosity at low temperatures and insufficient resistance to the action of fluids at elevated temperatures, in addition, it is hydrophobic and is unable to gain a foothold in the "fracturing" of water.

Another technical solution for insulation and casing and also associated with the use of alkylresorcinol resin (A.S. USSR №1629479, EV 33/138, bull. No. 7, 1991), contains additional epoxygenase resin alcohol solution of phenol-formaldehyde Novolac resins, butyral and furfural, which are entered into cooperation for carrying out modification (forcedevice). The disadvantage of this structure is that the presence of solvents - alcohol and furfural during curing will not allow to evaporate the solvent and to obtain a solid polymer, and therefore it is insufficient resistance to aggressive media, especially to acid.

An improved modification of the epoxy resin (EN 2128677, C08G 59/14, C09K 8/44, bull. No. 10, 10.04.1999 g) obtained by blending epoxygenase and any phenol-formaldehyde resin, polyvinyl alcohol, formalin and diethylene glycol. This modification is not suitable for plugging wells from water production during drilling and sealing of joints in operation since cures amines for 5-6 hours, during this time, the water inflow will all wash away. Used as a floor, not a waterproofing or backfill, therefore, in the description of this specified.

By A.S. USSR №1747678, E21B 33/128, 1992 for plugging water influx into the well a mixture of silicone resin and hydrochloric acid, which is currently prohibited on the basis of sanitary-hygienic hazard to groundwater. In addition, after exposure of the composition in the reservoir for 16-24 hours permeability wells only be reduced by 20-25%, which can cause erosion and ablation in groundwater.

For the same reason, difficult to use solutions A.S. USSR 765497, E21B 33/13, where the composition is used methacrylic acid, epichlorohydrin as gelling and water. The gel formation a composition from two to ten days and this is the syneresis of the gel (the phenomenon of spontaneous reduction gel with simultaneous separation of outward dispersion cf the water). The epichlorohydrin - burning skin liquid containing chlorine and epoxy group, and this is the 1st class of hazard. Components may get into the soil and aquifers, and then to appear in reservoirs and wells.

Known composition to isolate water production and acquisitions in wells (A.S. USSR №1176063, E21B 33/138, bull. No. 32 of 30.08.1985 g)containing a copolymer of sodium methacrylate and methacrylic acid, and instead of epichlorohydrin used water-soluble aliphatic epoxy resin based on triethylene glycol TEG-1, so the proposal can take the closest analogue to offer. To reduce the time of gelation accelerator is used the UE 606/2 (2,4,6-tridimensionality). According to the cited source, it is not known whether he cures with the required speed in the presence of salts and acids. However, it is known that resin TAG-1 does not allow to obtain a solid polymer structure, opposing loads of water, and when drilling out cement plugs he can gather around a drill and open water inflow.

A common drawback of all the above analogues, like most similar to the proposed technical solution is that it does not take into account the ability of the aquifer in contact with the compound to wash a large part of the water-soluble component - usually it definitely is yet reactivity - therefore, the backfill properties are manifested over a long time. In addition, because this does not form a strong adhesive bond, i.e. attachment to the "fracturing" of the soil. Accordingly, the resistance to aggressive fluids in the borehole is also insufficient.

3. The invention

The challenge when creating compound to improve adhesion and cohesion strength in the process of plugging, chemical resistance, eliminating the toxicity of the used components and software technology in the field, especially in winter, is solved by the invention.

Compound epoxidations Volosovsky cement, which is a set of epoxydodecane resin base and hardener amine type, characterized in that epoxydodecane tar obtained by epoxydecane aromaticheski conjugated hydroxyproline having a degree of polycondensation n=2, obtained at a temperature of 240-260°C from diatomic phenol (alkylresorcinol) diglycidyl ether of diethylene glycol with a degree of polycondensation n=0-2, when a molar ratio of 1:5. Epoxidation is carried out in the melt at 120-165°C in the presence of 0.15 and 0.35 wt.% 2,4,6-tridimensionality to the masses. the proportion of epoxy groups 6,0-9,0% and an additional resin portion contains 15-25 wt.% technical water. Content is the ingredients in the kit compound, parts by weight of:

- the above resin part100
- hardener amine type2,0-12,0.

The compound also differs in that its set as a hardener of amine type, depending on the season of application and the specifics of plugging water production consists of: 100 parts by weight of resin parts it contains in parts by weight from 2.0 to 2.7 Diethylenetriamine and/or from 3.2 to 5.0 polyethylenepolyamine, and/or from 5.2 to 6.0 aminophenol AF-2, and/or from 10.0 to 12.0 gamma aminopropyltriethoxysilane, and/or from 10.0 to 11.0 of diaminodiphenylmethane, and/or mixtures thereof, and/or other structures, used for curing epoxy resins.

On inventive step in the development of the resin part of the compound was found that by dissolving it (resin parts) in water after synthesis, they are combined without stratification and withstand peregorazhivanie at a temperature of minus 30°C.

During curing compound with a water content of more than 25 wt.%, containing salt, acid, oil and other impurities, also not is stratification, which is very effective in the formation of the tamping tube. In addition, the resin part in the formation of polymer during curing components are not washed out, but on the contrary, the nab is the Chania its still up to 30% of the volume.

The main parameters of the resin part and the compound shown in the table.

Table
№ p/pThe name of the parameter
1AppearanceLiquid dark brown
2Mass fraction of non-volatiles, %:
for compound 80 concentration80±2
for compound 100 concentration95-100
3Mass fraction of epoxy groups %6-9
4The density of 50% solution of compound1,108 g/cm3
The density of a 60% solution of the compound1,135 g/cm3
5Kinematic viscosity
- 50% solution of compound 267 mm2/s
- 60% solution of the compound800 mm2/s

The curing compound with a hardener in 6-10% aqueous salt solution and the oil is without complications.

Adhesion to the metal surface of the pipe tubing (tubing) for injection to the place of plugging minor, Zemlyane surface of the tube occurs.

Adhesion to tamponirovanie surface - fracture problem areas - provides a solid grip without leaching and provides a low permeability.

When used as a hardener polyethylenepolyamine (PEPA) depending on the concentration of the compound is changing the curing time of 90 min (at 80% concentration) to 365 minutes (with a 40% concentration) at 20°C and 40 min at 60°C to 80 min at the above concentrations.

Thus, changes in the concentration and temperature can vary cement composition depending on the conditions and tasks.

Raw materials:

epoxy resin deg-1;

- oligomer ARGOV-3;

accelerator 2,4,6-tridimensionality brand K-54;

the hardener is a polyethylenepolyamine (Pepa); gamma aminopropyltriethoxysilane; aminophenol AF-2; diaminodiphenylmethane;

- water technical water supply or the gang.

The toxicity of the compound - General, as when working with epoxy resins. Fire hazard, explosion hazard during storage, transportation and work is available.

The compound upon receipt (synthesis) is freed from traces of epichlorohydrin (ECG), contained in very small quantities in any of the epoxy resins. ECG when the synthesis is removed and reacts with the hydroxyl of alkylresorcinol, and when combined with water, the water is not separated from the compound when moving in the pipe and curing, so the release of harmful substances into the environment is reduced to the minimum quantities that production conditions is not significant.

The range of boundary values of components in the synthesis of compound selected to provide technological and operational characteristics, as during storage, transportation, loading, and operating to reduce water production in the well. Hardeners and accelerators are selected empirically as well as for all epoxy compounds, known methods. Videofestival with the compound by its nature and technology needs may change in water content of from 15 to 25 wt.%, and in particular cases on the proposed decision is up to 60 wt.%. The compound may be supplied with water both in summer and winter, so as to withstand the PE marajuana. Delivery may be without water, but when dissolved requires heating to 20°C and intensive mixing. The number of input hardeners re-calculated on the dry matter, and they may be introduced into the solution.

Thus, the proposed solution has the advantage over the known, accepted for analogue and provides the customer's request for elimination of water in the well, thereby increasing well production, reduces costs plugging, not complicate the environment in the extraction of oil and gas.

1. Compound epoxidations Volosovsky cement, which is a set of epoxydodecane resin, as resin and hardener of amine type, characterized in that the epoxy resin base obtained by epoxydecane aromaticheski conjugated hydroxyproline having a degree of polycondensation n=2, obtained at a temperature of 240-260°C from diatomic phenol (alkylresorcinol) diglycidyl ether of diethylene glycol with a degree of polycondensation n=0-2 when a molar ratio of 1:5, epoxidation is carried out at a temperature of 120-165°C in the presence of 0.15 and 0.35 wt.% 2,4,6-tridimensionality to wt. the proportion of epoxy groups 6,0-9,0% and an additional resin portion contains 15-25 wt.% technical water and the contents of the ingredients in the composition to which plecta compound is parts by weight:

the above resin part100
the amine hardener typeof 2.0 to 12.0

2. The compound according to claim 1, characterized in that it is set as a hardener of amine type, depending on the season of application and the specifics of the plugging of water per 100 parts by weight of resin parts contains parts by weight of: from 2.0 to 2.7 Diethylenetriamine, and/or from 3.2 to 5.0 polyethylenepolyamine, and/or from 5.2 to 6.0 aminophenol AF-2, and/or from 10.0 to 12.0 gamma aminopropyltriethoxysilane, and/or from 10.0 to 11.0 of diaminodiphenylmethane, and/or mixtures thereof and/or mixtures thereof, and/or other structures, used for curing epoxy resins.



 

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1 tbl

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