Geopolymer composition capable of pumping, which is meant to be used in oil industry

FIELD: oil and gas industry.

SUBSTANCE: suspension to be used in oil and gas wells, which contains the following components: aluminium silicate source, carrying fluid, activator of the group including metal silicate, metal aluminate, alkaline activator or their combinations. At that, suspension is capable of being pumped with the composition with such rheological properties that its viscosity is 300 CP or less, and suspension can be cured in well conditions.

EFFECT: obtaining geopolymer suspensions with possibility of monitoring the thickening and hardening periods of time for wide temperature intervals and density, which are capable of being pumped and used for well cementing.

43 cl, 11 tbl, 4 ex

 

The technical field to which the invention relates

This invention generally relates to well cementing. More specifically, this invention relates to the use of geopolymers, geopolymeric compositions capable of pumping, and methods of placing geopolymeric compositions in the well using conventional or special technologies cementing.

Geopolymer are a new class of materials, which are formed by chemical dissolution and subsequent recondensation various aluminosilicate oxides and silicates with the formation of an amorphous three-dimensional frame structure. Therefore, geopolymer is a three-dimensional aluminosilicate mineral polymer. The term "geopolymer" was proposed and first used by J. Davidovits (Synthesis of new high temperature geopolymers for reinforced plastics/composites, SPE PACTEC 79, Society of Plastics Engineers) in 1976 at the Symposium IUPAC International Symposium on Macromolecules held in Stockholm.

Geopolymer based on silicates, called poly(salatami), which is a shorthand name for poly(silicon-oxo-aluminate) or (-Si-O-Al-O-)n (where n represents the degree of polymerization). The mesh structure salata consists of tetrahedra SiO4and AlO4with a dense covering connected alternately by sharing all of the oxygen atoms in IV-fold koordinira the NII Al 3+and Si4+with oxygen. Positively charged ions (Na+, K+Li+Ca2+...) must be present in the cavities of frame structure to balance the negative charges Al3+in IV-fold coordination.

Empirical formula policiales the following: Mn{-(SiO2)z-AlO2}n·wH2O, in which M represents a cation, for example potassium, sodium or calcium, n is the degree of polymerization and z is the atomic ratio Si/Al, which can be 1, 2, 3 or more, up to 35, as it is known today.

Geopolymer with three-dimensional (3D) mesh structure are summarized in Table 1 below.

Table 1: Chemical name geopolymers (where M represents a cation, for example potassium, sodium or calcium, and n is the degree of polymerization).

Mn(-Si-O-Al-O-Si-O)n
Table 1
The ratio Si/AlNameStructureDesignation
1Poly(Salat)Mn(-Si-O-Al-O-)n(M)-PS
2Poly(Salat-silox)(M)-PSS
3Poly(Salat-disiacs)Mn(-Si-O-Al-O-Si-O-Si-O-)n(M)-PSDS

Properties and applications of geopolymers will depend mainly on their chemical structure and, more specifically, from the atomic ratio of silicon and aluminum. Research geopolymers was conducted for use in several applications, including use as a cementitious material in the construction industry, as a refractory material and as sealing agents for hazardous and radioactive waste. Geopolymer also refer to the quick-setting and bystrozatverdevshikh materials. They have very high hardness and chemical stability.

Various prototypes reveal the use geopolymeric compositions in the construction industry. In particular, U.S. patent 4509985 reveals the mineral composition of the polymer used for the manufacture of cast or molded at room temperature or temperatures, usually up to 120°C; U.S. patent 4859367, U.S. patent 5349118 and U.S. patent 5539140 reveal geopolymer to translate into solid state and storage of waste, to ensure the high stability of waste for a very long period of time, comparable to some of the archaeological materials, such waste may be hazardous or potentially toxic for humans and the natural environment; U.S. patent 5356579, 5788762, 5626665, 5635292, 5637412 and 5788762 reveal cementitious systems with high compressive strength and low density for use in construction. Patent application WO 2005019130 is the first, which brings to the fore the problem with time adjustment setting geopolymeric system in the construction industry. In practice, because geopolymer have little time setting, you should use a retarder to increase this setting.

However, none of the prototypes were not discussed geopolymer for use in the oilfield industry. Although the patent application WO 2005019130 discloses a particular type of a new family of geopolymers with some retarding effect on the setting time for the construction industry, the real time control setting is not provided for all other geopolymeric systems. In addition, the potential use of cementitious systems in the oilfield industry is influenced by other acute technical problems. These problems are, for example, the control times of thickening and stiffening for a wide temperature range and tightly the ti geopolymeric suspension, suitability for mixing and its ability to pumping. Should also take into account other properties, such as compressive strength and permeability of the cured geopolymer material. It would therefore be desirable production geopolymers, resolving these problems and has good properties for use in the oilfield industry.

The invention

In one of the embodiments, the invention discloses a suspension containing the aluminosilicate source, a carrier fluid and an activator from the group comprising a metal silicate, a metal aluminate, alkali activator, or combinations thereof, and the suspension is capable of pumping a composition applicable in the oilfield industry, and the suspension has the ability to grasp the conditions of the wells. All three components need to be added separately: for example, the activator may already be present in the carrier fluid. Similarly, the source of the silicate may be in the form of a solid component; a metal silicate may be in solid form or in the form of a mixture of silicate of the metal in the carrier fluid; the activator may be in solid form or in the form of a mixture of activator in the carrier fluid. An important factor is the presence of a carrier fluid for the manufacture of suspen the AI, if the aluminosilicate source, a metal silicate and an activator are in solid condition. If the source of silicate and silicates of metals are in the solid state, while the activator is in a liquid state, the activator is considered as already containing liquid inside. In addition, it is clear that you do not want the carrier fluid was the only one, and possibly two or more liquid carriers. Geopolymer composition has such rheological properties that suspension specified geopolymeric composition has a high capacity for pumping and stability. Capable of pumping the composition into the oil industry has a rheology that its viscosity is 300 SP or less, preferably in another embodiment 250 of the JV or less, more preferably in yet another embodiment 200 of the JV or less. In addition, this suspension is stable suspension. Geopolymer composition suitable for mixing and capable of pumping; therefore, in most cases, it is possible its application in oilfield industry.

To regulate the setting time geopolymeric composition, choose alkaline activator with a given pH value and/or add retarder setting and/or add the accelerator to susp is nsii specified geopolymeric composition. Alkaline activator may be, as a rule, a hydroxide of an alkali metal, more preferably sodium hydroxide or potassium, and it can also be a carbonaceous material. The setting retarder is selected from the group comprising boron-containing compound, lignosulfate, sodium gluconate, glucoheptonate sodium, tartaric acid and phosphorus-containing compounds. Preferably, the retarder setting is anhydrous or gidratirovannym borate of an alkali metal, or pure boron oxide. More preferably, the setting retarder is desativada pentaborate sodium, boric acid or brown. The accelerator is a compound containing alkali metal, preferably lithium or potassium. Preferably, the accelerator is a salt of lithium. More preferably, the accelerator is lithium chloride. Control setting time is thus effective in the range from 20°C to 200°C. Desativada pentaborate sodium and borax provide control setting time of 20°C, preferably from 25°C to 150°C.

To regulate the setting time geopolymeric composition, type of aluminosilicate choose a specific way, depending on the temperature of application.

To regulate density geopolymer composition can be added to light particles and/or heavy particles. Light hour the Itza, also called fillers are selected from the group including cenospheres, ceramic, sodium-calcium-borosilicate glass and aluminosilicate microspheres. Heavy particles, also called weights are generally chosen from the group including manganese tetroxide, iron oxide (hematite), barium sulfate (barite), silica, and iron oxide/titanium (ilmenite). Geopolymer compositions can also be foamed by a foaming suspension specified geopolymeric composition gas such as air, nitrogen or carbon dioxide. Geopolymer composition may also contain gas-forming additive, which will enter the gas phase in suspension. Preferably, the density of the suspension of these geopolymeric compositions varies between 1 g/cm3and 2.5 g/cm3, more preferably between 1.2 g/cm3and 1.8 g/cm3.

In the second embodiment, the suspension specified geopolymeric composition may also contain a mixture of two or more sources of aluminum silicate. In yet another embodiment, the suspension specified geopolymeric composition may contain a second component of the binder, which may be a conventional cementitious material such as Portland cement, super fine grain cement or finely dispersed silica.

In the third embodiment, the suspension specified polimernoi composition may contain a gas phase so what gas phase or part of the gas phase remains in geopolymeric composition. For example, the gas phase may be the dispersed phase nitrogen is not miscible with water.

In the fourth embodiment, the suspension specified geopolymeric composition may contain a phase that is not miscible with water. For example, this may be the dispersed oil phase is not miscible with water.

In the fifth embodiment, geopolymer composition also contains an additive selected from the group comprising: an activator, non, antifoam, silica, additive for regulating water loss, additive to improve fluidity, a dispersant, a rheology modifier, a blowing agent, surfactant and additive preventing the deposition.

Geopolymers the compositions of this invention are preferably compositions containing poly(Salat), poly(Salat-silox) or poly(Salat-disiacs) components. More preferably, geopolymer compositions include poly(Salat-silox) components, and therefore, the atomic ratio of silicon and aluminum, as a rule, is equal to 2, in the range from 1.8 to 2.8.

Another feature of this invention is the suspension containing the aluminosilicate source, a carrier fluid, the activator from the group comprising: a metal silicate, aluminate meta is La, alkaline activator, or combinations thereof, and the moderator setting, able to slow the thickening and/or stiffening the suspension, and/or accelerator capable of accelerating the thickening and/or stiffening of the suspension, in which the metal is an alkali metal, and the molar ratio of the oxides of M2O/SiO2is more than 0.20, while M is the specified metal.

In the case of setting retarder it is preferably a compound containing boron, and suspension specified geopolymeric composition preferably has a molar ratio of oxides of B2O3/H2O less than 0.03.

In the case of using the accelerator, it is preferably a compound containing lithium or potassium. Suspension specified geopolymeric composition preferably has a molar ratio of oxides of Li2O/H2O less than 0.2. More preferably, the composition geopolymeric suspension has a molar ratio of oxides of Li2O/H2O of 0.1 or less.

In geopolymeric compositions according to this invention uses a source of silicate, which is selected from the group comprising fly ash type C according to ASTM, fly ash type F according to ASTM, crushed blast furnace slag, clay, and partly of baked clay such as metakaolin), finely dispersed silica, the content is of ASI aluminum, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, volcanic slag, allion, bentonite and pumice. Preferably, geopolymer composition made with the use of metakaolin, kaolin, ground granulated blast furnace slag and/or fly ash.

In geopolymeric compositions according to this invention uses a metal silicate selected from the group comprising lithium, sodium, potassium, rubidium and cesium. Preferably, the metal is sodium or potassium. In another embodiment, the silicates of metals can be replaced by ammonium silicates. The metal silicate in another embodiment, may be encapsulated.

In geopolymeric compositions according to this invention as an alkaline activator is used, for example, a hydroxide of an alkali metal. Preferably, the alkali metal hydroxide is sodium hydroxide or potassium. Alkaline activator and/or the metal silicate can be encapsulated. Carbonates of alkali metals can also be used as the alkaline activator. In addition, the alkaline activator in another embodiment, may be encapsulated.

In geopolymeric compositions according to this invention as a carrier liquid is preferably used an aqueous solution, for example fresh water.

In accordance with another feature of the present invention disclosed a method of regulating the setting time geopolymeric suspension for the oilfield industry. The method includes a step of providing a suspension in the carrier fluid by adding: (i) moderator and/or accelerator setting; (ii) source of aluminosilicate; (iii) activator from the group comprising a metal silicate, a metal aluminate, alkali activator, or combinations thereof. The preceding stages can be performed in a different order. Geopolymers the compositions of this invention prepared in this way are controlled by the time setting at temperatures from 20°C up to at least 200°C. Used geopolymer composition - the same that are described above. While the alkaline activator is selected from the group comprising: sodium hydroxide and potassium hydroxide; the setting retarder is selected from the group comprising boron-containing compound, lignosulfate, sodium gluconate, glucoheptonate sodium, tartaric acid and phosphorus-containing compounds.

To regulate the times of thickening and/or setting geopolymeric composition, changing the appearance and/or pH and/or concentration of the activator, and/or the concentration of the metal silicate. By increasing the concentration of the activator, the setting time is reduced and by changing the type and/or pH to get a different time setting. To adjust the time of thickening geopolymeric composition, changing the appearance is/or concentration of retarder setting. By increasing the concentration of retarder setting time and increase it by changing its type to get a different time setting. Similarly, in order to regulate the setting time geopolymeric composition, changing the appearance and/or the concentration of the accelerator. By increasing the concentration reduce the setting time and by changing its type to get a different time setting. As you can see, there are three solutions to regulate the setting time, the use of a special activator, the use of a setting retarder or accelerator setting. These three solutions can be used individually or in combination. Sometimes the use of a special activator does not provide a large enough setting time, and the use of retarder setting may be preferred. Similarly, the use of a special activator may not provide enough short setting time, and it would have been preferable to the use of the accelerator.

In accordance with another feature of the present invention disclosed a method of adjusting the density of the suspension for the oilfield industry. The method includes a step of providing a suspension in the carrier fluid by adding: (i) lay the of the particles and/or heavy particles; (ii) source of aluminosilicate; (iii) alkaline activator from the group comprising: a metal silicate, a metal aluminate, alkali activator, or combinations thereof. The preceding stages can be performed in a different order. In addition, in accordance with another feature of the present invention the method also includes the stage of adding to the suspension retarder and/or accelerator setting. In addition, in accordance with another feature of the present invention the method also includes the stage of foaming suspension specified geopolymeric composition.

In accordance with another feature of the present invention disclosed a method of adjusting the density of the suspension for the oilfield industry, this method includes the following stages: (i) provide such a suspension in the carrier fluid by mixing aluminosilicate source, a metal silicate and an activator from the group comprising: a metal silicate, a metal aluminate, alkali activator, or combinations thereof, with a liquid carrier, (ii) foaming suspension specified geopolymeric composition. In addition, in accordance with another feature of the present invention the method also includes the stage of adding to the suspension retarder and/or accelerator setting.

The method of regulating the density geopolymeric compositions according to this invention is applied on the I interval densities of 1 g/cm 3up to 2 g/cm3but also can be applicable for the range of densities from 0.8 g/cm3to 2.5 g/cm3.

In accordance with another feature of the present invention disclosed a method of placing geopolymeric composition in a borehole and the isolation of the subterranean earthen formations, the method includes the following stages: (i) providing a suspension described above, (ii) pumping the specified suspension in a borehole, and (iii) enabling the setting of the specified suspension in the well conditions and thereby forming geopolymeric composition.

In another embodiment, the stage of grant of suspension specified geopolymeric composition also includes adding retarder setting and/or accelerator and/or activator. In practice, it may be helpful to slow setting geopolymeric composition by adding retarder setting, as shown above, and/or may be useful acceleration setting geopolymeric composition by adding accelerator, as shown above.

In addition, in another embodiment, the method comprises a stage of activation of suspension specified geopolymeric composition in situ. In practice, this method also applies if the activation must be performed in the well, and activation neobyazatel is associated with the alkaline activator. In fact, in the first embodiment, activation refers to the activation by alkaline activator, and an alkaline activator is encapsulated, as described above, or is released by the downhole device. In the second embodiment, activation refers to any type of activation, when used various additives required for activation, for example, activation may be physical (heat, irradiation with UV radiation or radiation of a different species); activation can also be done with the use of chemical components that are encapsulated and released after a certain period of time or when creating the specified conditions. Capsules can be broken spontaneously, as explained above, or may be destroyed by the application of mechanical stresses and/or acoustic disturbance.

In the first embodiment, the setting time geopolymeric composition increased significantly, so that must be met activation to cause adhesion geopolymeric composition. The activation occurs when the release of the activator. This release is in the borehole, in situ, by the addition of the activator directly to the suspension specified geopolymeric composition and/or if the activator is encapsulated in suspension specified geopolymeric whom is osili, the destruction of the capsules.

In addition, in another embodiment, the method comprises a stage of activation of suspension specified geopolymeric composition immediately prior to use. For example, inactivated suspension geopolymeric composition is made so that the suspension is stable for a long time. This composition has the ability to store and to transport a slight degradation after passing the period of time from one day to several months, preferably from several days to three months. The suspension is capable of storing, delivered to the drilling rig in a liquid form and is activated prior to injection or in the borehole in situ, as discussed above.

Preferably, the phase of injection of suspension specified geopolymeric composition is performed using conventional equipment for well cementing, well-known experts in this field. The method is applicable as technology primary cementing cementing, in which geopolymer composition is pumped by the well column pipe to the casing Shoe and then rises through the annular space between the casing pipe/casing liner and the wellbore. Technology cementing with skim milk the second circulation can also be used to accommodate suspension geopolymer at the desired depth in a borehole.

In addition, the injection and the placement of the suspension geopolymer below the surface covers several other conventional cementing technologies, such as the pouring of cement mortar piles or skirts stationary offshore platform or the like, the sealing operation for repair or plugging for eliminating unwanted leaks, perforation, molding or the like, as well as setting caps from geopolymeric composition in the case of cement plugs for any purpose.

These methods also apply to host geopolymeric composition to seal the area of the borehole. The methods are applicable for water wells, geothermal wells, injection wells for steam injection into the reservoir, wells with directional air injection (Toe to Heel Air Injection - THAI) and wells with acid gas. Composition, as such, can withstand temperatures above 250°C, even higher than 450°C and 550°C.

Brief description of drawings

Other embodiments of the present invention can be understood by using the supplied drawings:

Figure 1 represents the effect of temperature on the time of thickening geopolymeric compositions.

Figure 2 represents the effect of adding an accelerator to the time of thickening geopolymeric compositions.

In accordance with this invention geopolymer compositions include the source is alumosilicate, the metal silicate and alkali activator in the carrier fluid at a temperature close to ambient temperature. The carrier fluid is preferably a solution on the basis of fresh water. As described above, all the four component does not have to be added separately: for example, the alkaline activator may already be in the water. Similarly, the source of the silicate may be in the form of a solid component; a metal silicate may be in solid form or in the form of an aqueous solution of metal silicate; alkali activator may be in solid form or in the form of an aqueous solution of alkaline activator.

Part geopolymer concrete is the source of the aluminosilicate. Examples of aluminosilicate source, which can be formed geopolymer include fly ash type C according to ASTM, fly ash type F according to ASTM, crushed blast furnace slag, clay, and partly of baked clay such as metakaolin), fine silica containing aluminum, natural aluminum silicate, synthetic aluminosilicate glass powder, zeolite, volcanic slag, allion, bentonite and pumice. These materials contain a large fraction of amorphous aluminosilicate phase, which reacts with strong alkaline solutions. The preferred aluminosilicates are fly ash, IU akalin, kaolin and blast furnace slag. If necessary, can also be used a mixture of two or more sources of aluminum silicate. In another embodiment, component aluminosilicate contains the first aluminosilicate binder and optionally one or more components of the second binder, which can be selected from the group including: crushed, granulated blast furnace slag, Portland cement, kaolin, metakaolin, or finely dispersed silica.

Part geopolymeric material may also include alkaline activator. The alkaline activator is usually a hydroxide of an alkali metal. Hydroxides of alkali metals are, as a rule, the hydroxides of sodium and potassium. The metal hydroxide may be in the form of a solid substance or in the form of an aqueous mixture. In addition, the alkaline activator in another embodiment, may be encapsulated. Alkaline activator when it is present in solid and/or liquid state can be maintained in capsules, which are destroyed when they are exposed to, for example, the effects of stress or radiation. In addition, the alkaline activator when it is present in solid and/or liquid state can be maintained in capsules, which are destroyed in a natural way, for example due to the fact that the capsules are made of biodegradable and/elisamarcushooker material. In addition, when the alkaline activator is in a liquid state, it can be adsorbed on the porous material and be released after a certain period of time or when creating the specified conditions.

Part geopolymeric material may also include a silicate or aluminate metal or a combination of different silicates and aluminates of metal. The metal silicate is typically a silicate of an alkali metal. Preferred are the alkali metal silicates, particularly sodium silicate or potassium silicate. Preferred are sodium silicate with a molar ratio of SiO2/Na2O components of 3.2 or less. Preferred are the potassium silicate with a molar ratio of SiO2/K2O components of 3.2 or less. In addition, in another embodiment, the metal silicate can be encapsulated.

The method according to this invention is applicable in the field of oil industry, preferably in the completion of oil or gas wells. For use in the oilfield industry to form the composition of geopolymer capable of pumping, in which the components are mixed with the carrier fluid. To a suspension can be added various additives, and then the slurry may be pumped into the wellbore. The suspension is then incubated for grasping in the borehole,providing isolation layers in the wellbore.

The method of placing geopolymer

Typical property geopolymeric systems is their ability to hardening without delay after mixing. However, for use in the oilfield industry requires geopolymer suspension, suitable for mixing and capable of pumping. For this reason, you need a way to slow the thickening geopolymeric suspension or method of regulating the time of thickening of geopolymer.

Found a wide range of retarders, providing the slow stiffening of geopolymer. Table 2 presents the results of tests on the thickening time, when using a consistometer at high temperature and under high pressure (HPHT) in accordance with the recommendations of ISO 10426-2. Such tests are performed to simulate the placement of the cement slurry from the surface into the well at a certain temperature of the circulating fluid at the well bottom (BHCT). To perform these tests the temperature rises thus, in order to simulate the placement in real well. For tests performed at 57°C, this temperature was achieved through 41 minute, and final pressure amounted to 33.8 MPa (4900 pounds per square inch). For tests performed at 85°C, this temperature was achieved in 58 minutes, and the final pressure is left with 55.1 MPa (8000 pounds per square inch). For tests performed at 110°C, this temperature was achieved in 74 minutes, and the final pressure was 75,9 MPa (11000 lbs/square inch).

Table 2: Examples of values of thickening ISO 10426-2, measured by HPHT consistometer (hours:min)for different retarders at different temperatures.

td align="justify"> 2
Table 2
Temperature (°C)5785110
SampleA2A2B2C2D2
Moderator setting% by weight of the mixtureThe thickening time
No06:250:530:37 5:451:40
Na2B10O16, 10H2O0,656:303:00
1,323:526:08
1,67:30
1,810:399:51
13:05
2,628:23
H3BO31,920:53
Phosphonate/pentabarf sodium1,27:00 PM
Phosphonate/phosphate salt6,4>15:00
Lignosulfonate1,513:12

Sample A2 was produced by dissolving an appropriate quantity of retarder setting in 358 g of water, adding a mixture containing 314 g of metakaolin and 227 g of disilicate sodium in the solution under stirring, the addition of 17.2 g of sodium hydroxide under stirring ISO 1026-2 and pouring the suspension in the HPHT cell. Sample A2 was then tested by measuring the time of thickening the HPHT consistometer.

Sample B2 was produced by dissolving an appropriate quantity of retarder setting in 265 g of water, adding a mixture containing 232 g of metakaolin, 168 g of disilicate sodium and 414 g of silica as a filler in the solution under stirring, adding 13 g of sodium hydroxide under stirring ISO 10426-2 and pouring the suspension in the HPHT cell. Sample B2 was then tested by measuring the time of thickening the HPHT consistometer.

Sample C2 was made by dissolving the appropriate amount the VA setting retarder in 422 g of sodium hydroxide solution by the addition of a mixture containing 440 g of fly ash type F and 88 g of disilicate sodium in the solution under stirring, followed by stirring at ISO 10426-2 and pouring the suspension in the HPHT cell. Sample C2 was then tested by measuring the time of thickening the HPHT consistometer.

Sample D2 produced by dissolving an appropriate quantity of retarder setting in 374 ml of water by addition of a mixture containing 411 g fly ash type F and 82 g of disilicate sodium with stirring at 4000 rpm, the addition of 75 g of sodium hydroxide under stirring ISO 10426-2 and pouring the suspension in the HPHT cell. Sample D2 then tested by measuring the time of thickening the HPHT consistometer.

Slow setting geopolymeric compositions can be controlled at different temperatures of the circulating fluid at the well bottom (BHCT) through the use of either boron-containing compounds, for example desativado of pentaborate sodium, boric acid, borax or lignosulfonate, or phosphorus-containing compounds, or mixtures thereof. Slow setting geopolymeric compositions will depend on the valency of boron in the boron-containing compounds or valence of the phosphorus in the phosphorus-containing compounds and/or concentration of retarder setting.

Table 3 presents the results obtained for the two retarders bases on the boron in the use of the device Vico. The device Vico allows you to define the beginning of the seizure (IST) and its end (FST). The principle of its operation is based on measurements of the penetration of the needle into the soft material. This device is often used for preliminary studies under ambient temperature and atmospheric pressure.

Table 3: Examples start time setting (hours:min), defined for different retarding device Vico at ambient temperature and atmospheric pressure.

Table 3
SampleA3B3
Without additives1:4512:00
Na2B10O16, 10H2O
of 2.6% by weight of the mixture3:00-
5.2% of the mass of the mixture4:10>500:00
Borax
of 4.2% by weight of the mixture3:20 -

Sample A3 was produced by dissolving an appropriate quantity of retarder setting in 139 g of sodium hydroxide solution and the addition of a mixture containing 105 g of metakaolin, 48 g of sodium metasilicate and 17 g of silica as a filler in the solution with stirring. Sample A3 then tested by pouring the suspension into the cell device Vico to measure the setting time at 25°C.

Sample B3 was produced by dissolving an appropriate quantity of retarder setting in 358 g of water, adding a mixture containing 314 g of metakaolin and 227 g of disilicate sodium in the solution with stirring and the addition of 17.2 g of sodium hydroxide under stirring ISO 10426-2. Sample B3 then tested by pouring the suspension into the cell device Vico to measure the setting time at 25°C.

Slow setting geopolymeric compositions sensitive to temperature. However, the two retarder setting on the basis of boron (desativada pentaborate sodium and borax) can significantly slow down the setting of suspensions of geopolymer different species even at 25°C.

Figure 1 illustrates the effect of temperature on the thickening time for geopolymeric composition produced by adding a mixture containing 411 g fly ash type F and 82 g of disilicate sodium, 374 ml of water under stirring (moderator setting p is evritania has dissolved in the water) and added 36.5 g of sodium hydroxide under stirring ISO 10426-2. When the retarders are effective even at high temperature, providing a time control of thickening suspension geopolymer.

The time control gel can also be implemented by other means. For example, at the time of thickening is influenced by the type of alkaline activator and its pH. Table 4 illustrates the effects of alkaline activator at the time of thickening geopolymeric suspensions. This demonstrates the possibility of selecting a source of alkaline activator in accordance with the conditions of the well.

Table 4: Examples of time-thickening, measured according to ISO 10426-2 using HPHT consistometer (hours:min)with different alkaline activators and measured at 85°C.

Table 4
SampleA4B4
100 Bc (units Berdina)0:53>31:00

Sample A4 was produced by addition of a mixture containing 314 g of metakaolin and 227 g of disilicate sodium, 358 g of water under stirring, the addition of 17.2 g of sodium hydroxide under stirring ISO 10426-2 and pouring the suspension in the HPHT cell. Sample A4 was then tested by measuring the time of gelled consistenet the om obtained.

Sample B4 was produced by addition of a mixture containing 314 g of metakaolin and 227 g of disilicate sodium, 357 g of water under stirring, the addition of 23.4 g of sodium bicarbonate with stirring ISO 10426-2 and pouring the suspension in the HPHT cell. Sample A4 was then tested by measuring the time of thickening the HPHT consistometer.

The control times of thickening and stiffening of these methods deceleration setting can also be effectively performed for geopolymer having a different ratio of silicon and aluminum.

In addition, depending on the properties of geopolymer, it may be appropriate to accelerate the thickening of the suspension. Table 5 illustrates the accelerating effect of lithium compounds at the time of thickening geopolymeric suspensions at a temperature of 85°C. This demonstrates the possibility of using lithium salts for controlling the time of thickening geopolymeric suspensions.

Table 5: Examples of values of thickening ISO 10426-2, measured by HPHT consistometer (hours:min), when using fly ash type F and accelerators.

Table 5
SampleA5B5
Without additives22:7 5:21
LiCl
a 3.5% by weight of the mixture9:07 am-
7% by weight of the mixture4:07
LiOH, H2O
2% by weight of the mixture-3:19

Sample A5 produced by adding a mixture containing 480 g of ultrafine fly ash type F and 96 g of disilicate sodium, 406 g of sodium hydroxide solution containing the accelerator, followed by stirring at ISO 10426-2 and pouring the suspension in the HPHT cell. Sample A5 then tested by measuring the time of thickening the HPHT consistometer.

Sample B5 produced by adding a mixture containing 442 g standard fly ash type F and 88 g of disilicate sodium, 423 g of sodium hydroxide solution containing the accelerator, followed by stirring at ISO 10426-2 and pouring the suspension in the HPHT cell. Sample B5 then tested by measuring the time of thickening the HPHT consistometer.

Figure 2 illustrates the accelerating effect of lithium compounds at the time the I of thickening the composition of geopolymer, made by adding a mixture containing 480 g of ultrafine fly ash type F and 96 g of disilicate sodium, 406 g of sodium hydroxide solution containing the accelerator, followed by stirring at ISO 10426-2. Then measured the time of thickening depending on the time of the suspension at a temperature of 85°C. While accelerators, such as lithium salts, showed effective reduction of the time of thickening geopolymeric suspensions. The degree of acceleration setting geopolymeric compositions depends on the type of accelerator and/or its concentration.

Depending on the properties of geopolymer and well properties can be set real time control of thickening of the suspension. To increase the time of thickening can be changed the type of setting retarder, can be increased concentration of the inhibitor can be changed the type of the alkaline activator, and may change the type of aluminosilicate.

In addition, when geopolymer suspension is intended for use in the oilfield industry, geopolymer suspension must be capable of pumping. Table 6 below illustrates the rheological properties geopolymeric suspensions, measured at the temperature of the circulating fluid at the well bottom (BHCT) at 60°C. the Values of the rheological characteristics of the dem will starout ability to pumping and stability geopolymeric suspensions for use in the oilfield industry.

Table 6: Measurement according to ISO 10426-2 rheological properties and stability for different samples.

Table 6
SampleA6B6C6
PV/TY (plastic viscosity/shear stress) after mixing49/1062/4105/7
ISO 10426-2 PV/TY when the temperature of the circulating fluid at the well bottom (BHCT)
SP/lb/100 sq. ft.
48/753/285/7
Free liquid ISO 10426-2 (ml)000

Sample A6 produced by adding a mixture containing 411 g fly ash type F and 82 g of disilicate sodium, 374 ml of water with stirring and the addition of 75 g of sodium hydroxide under stirring. Sample A6 then tested by determining the rheological properties of a suspension after mixing and after aging at 60°C in accordance with standard procedure ISO 1026-2.

Sample B6 produced by the dissolution of 0.65% tenth the water pentaborate sodium by weight of the mixture in 422 g of sodium hydroxide solution by the addition of a mixture containing 440 g of fly ash type F and 88 g of disilicate sodium in the solution under stirring ISO 10426-2 and added 36.5 g of sodium hydroxide under stirring. Sample B6 then tested by determining the rheological properties geopolymeric suspension after mixing and after aging at 60°C in accordance with standard procedure ISO 10426-2.

Sample C6 produced by adding a mixture containing 480 g of fly ash type F and 96 g of disilicate sodium, 406 g of sodium hydroxide solution, followed by stirring at ISO 10426-2. Sample C6 then tested by determining the rheological properties of a suspension after mixing and after aging at 60°C in accordance with standard procedure ISO 1-0426-2.

Table 7 presents the difference between the setting time in accordance with the terms of the setting. Geopolymer composition will seize faster in static than in dynamic conditions. Usually geopolymer suspension will quickly seize after placement.

Table 7: Example of comparison time setting (hours:min) in dynamic and static condition at 85°C.

Sample A7 produced by adding a mixture containing 440 g of fly ash type F and 88 g of disilicate sodium, 422 g of water with stirring followed peremeci what W ISO 10426-2 and pouring the suspension in the HPHT cell or cell device Vico.

Sample B7 produced by adding a mixture containing 442 g standard fly ash type F and 88 g of disilicate sodium, 424 g of sodium hydroxide solution containing 2% LiOH.H2O by weight of the mixture, followed by stirring at ISO 10426-2 and pouring the suspension into the HPHT consistometer or cell device Vico.

In addition, when geopolymer suspension is intended for use in the oilfield industry, geopolymer suspension should have a wide range of densities. As shown in Table 8, tested geopolymer compositions have a density in the range from 1.45 g/cm3(12.1 lb/Gal) up to 1.84 g/cm3(15.4 lb/Gal) or due to reduced water content, either due to the addition of fillers.

Table 8: Examples of the density of the suspension, obtained by using some geopolymeric compositions.

Table 8
SampleA8B8
The density of the suspension, g/cm3
pounds/gallon
1,84
(15,4)
1,44
(12,06)

Sample A8 produced by dissolving an appropriate quantity of retarder setting is 265 g of water by addition of a mixture containing 232 g of metakaolin, 168 g of disilicate sodium and 414 g of silica as a filler in the solution with stirring and the addition of 13 g of sodium hydroxide under stirring ISO 10426-2.

Sample B8 produced by dissolving an appropriate quantity of retarder setting in 139 g of sodium hydroxide solution and the addition of a mixture containing 105 g of metakaolin, 48 g of sodium metasilicate and 17 g of silica as a filler in the solution with stirring.

In addition, to expand the range of densities, add or light particles to obtain a lower density or heavy particles to obtain a higher density. Light particles typically have a density less than 2 g/cm3and, typically, less than 1.3 g/cm3. For example, you can use hollow microspheres, in particular aluminosilicate, known as cenospheres, ceramic, sludge generated from coal combustion and having the average particle diameter of about 150 microns. It is also possible to use synthetic materials such as hollow glass beads, and more specifically, preferred are granules of sodium-calcium-borosilicate glass, which have high compressive strength, or, of course, microspheres made of ceramics, for example, silica-alumina type. Light particles can be particles of plastic mater is Ala, for example, pellets of polypropylene. Heavy particles typically have a density of more than 2 g/cm3and, as a rule, more than 3 g/cm3. For example, you can use hematite, barite, ilmenite, silica and manganese tetroxide supplied to the market under the trade names MicroMax and MicroMax FF.

In addition, to extend the range of densities possible foaming of the composition of geopolymer. The gas used for foaming composition may be air or nitrogen, but nitrogen is most preferred. The amount of gas present in the cement composition is that amount which is sufficient to form a foam with a density in the range of from about 1 g/cm3to 1.7 g/cm3(from 9 to 14 pounds per gallon).

In another embodiment, in conjunction with geopolymers according to this invention can be used with other additives. In geopolymer compositions of embodiments of the invention may be incorporated additives, known to specialists in this field. Supplements usually are mixed with the base mixture or they can be added to the suspension of geopolymer. Additives may include, for example, activator, non, antifoam, silica, additive for regulating water loss, additive to improve fluidity, dispersant, additive preventing osuzhdeni is, or a combination of both. The choice of type and amount of supplements largely depends on the type and composition, and the usual experts in this field will be clear how to choose the appropriate type and quantity of additives for the compositions according to this invention.

In another embodiment, when other components are used with geopolymeric composition or particle size of the components is chosen in the optimization of the relevant share fractions of particles to provide the greatest volume fraction field (PVF) for solid substances and at the same time to get the suspension is suitable for mixing and capable of pumping, using minimal amounts of water, namely when volume concentration of solid substances (SVF) in the suspension component 35-75% and preferably 50-60%. Additional details can be found in European patent EP 0621247. The following examples do not limit the invention, but merely indicate the specialists in this area on the possible combinations of particle sizes of different components geopolymeric compositions according to this invention to produce a stable suspension, capable of pumping.

Geopolitika the composition may be "traversing" the combination of particles: "large", for example sand or crushed waste (average size of 100-1000 μm), "the medium is, for example, materials such as glass beads or other fillers (the average size of 10-100 μm), thin, such as, for example, fine-grained material or fine-grained ash dust or other fine-grained slag (the average size of 0.2-10 μm). Geopolymer composition can also be "chetyrekhmernoi" the combination of particles: large (average size of about 200-350 μm), "medium" glass granules or aggregates (average size of about 10-20 μm), thin (average size about 1 μm), very thin (average size of about 0.1 to 0.15 μm). Geopolymer composition may also be a different combination of particles of other types: "very large", for example sand for glass melting, crushed waste (average size exceeds 1 mm) and/or "big", such as sand or crushed waste (average size of about 100-1000 microns) and/or "medium", such as glass beads or fillers or crushed waste (average size of 10-100 μm) and thin, such as, for example, fine-grained ash dust or other fine-grained slag (the average size of 0.2-10 μm) and/or "very thin, such as, for example, latex or pigments or polymer microgels, such conventional fluid loss reducer (the average size of 0.05-0.5 µm) and/or "ultra-thin", such as some of colloidal silica or alumina (average size of 7-50 nm).

Mechanical stre is here

Mechanical properties under compression hardened geopolymeric compositions investigated using systems after curing for several days under high pressure and high temperature in the chambers with high pressure and high temperature to simulate conditions in oil or gas wells.

Tables 9 and 10 illustrate that geopolymer compositions described in this invention exhibit satisfactory compressive strength at low Jung module for use in the oilfield industry with the moderator or without it.

Table 9: Mechanical properties measured after conditioning for 7 days at 90°C and 20.7 MPa (3000 psig)

Table 9
SampleA9A9B9B9
Pentaborate sodium, % by weight of the mixture01,801,8
Tensile strength with unlimited compression (UCS), MPa1914 1513
The young's modulus, MPa2400210023003000

Sample A9 produced by dissolving the retarder setting (if used) 358 g of water, adding a mixture containing 314 g of metakaolin and 227 g of disilicate sodium in the solution under stirring, the addition of 17.2 g of sodium hydroxide under stirring ISO 10426-2, pouring the suspension in the form and placement of forms in the chamber for curing for 7 days at 90°C and 20.7 MPa (3000 psi) in accordance with the procedure of ISO 10426-2. Sample A9 then tested by measuring the compressive strength and young's modulus.

Sample B9 produced by dissolving the retarder setting (if used) in 265 g of water, adding a mixture containing 232 g of metakaolin, 168 g of disilicate sodium and 414 g of silica as a filler in the solution under stirring, adding 13 g of sodium hydroxide under stirring ISO 10426-2, pouring the suspension in the form and placement of forms in the chamber for curing for 7 days at 90°C and 20.7 MPa (3000 psi) in accordance with the procedure of ISO 10426-2. Sample B9 then tested by measuring the compressive strength and young's modulus.

Table 10: Mechanical with the STS, measured after incubation for 21 days at 90°C and 20.7 MPa (3000 psig)

Table 10
SampleA10B10C10
The lithium chloride, % by weight of the mixture037
Tensile strength with unlimited compression (UCS), MPa9,59,59
The young's modulus, MPa175025502950

Sample A10 produced by adding a mixture containing 482 g standard fly ash type F and 96 g of disilicate sodium to 408 g of sodium hydroxide solution containing the accelerator, followed by stirring at ISO 10426-2, pouring the suspension in the form and placement of forms in the chamber for curing for 21 days at 90°C and 20.7 MPa (3000 psi) in accordance with the procedure of ISO 10426-2. Sample A10 then tested by measuring the compressive strength and young's modulus.

Sample B10 produced by adding a mixture containing 442 g STD is bound fly ash type F and 88 g of disilicate sodium to 424 g of sodium hydroxide solution, containing 3% by weight LiCl mixture, followed by stirring at ISO 10426-2, pouring the suspension in the form and placement of forms in the chamber for curing for 21 days at 90°C and 20.7 MPa (3000 psi) in accordance with the procedure of ISO 10426-2. Sample B10 then tested by measuring the compressive strength and young's modulus.

Sample C10 produced by adding a mixture containing 480 g of ultrafine fly ash type F and 96 g of disilicate sodium, 406 g of sodium hydroxide solution containing 7% by weight LiCl mixture, followed by stirring at ISO 10426-2, pouring the suspension in the form and placement of forms in the chamber for curing for 21 days at 90°C and 20.7 MPa (3000 psi) in accordance with the procedure of ISO 10426-2. Sample C10 then tested by measuring the compressive strength and young's modulus.

Since the compositions of this invention exhibit high compressive strength with low Jung module, they could be very useful when used in the oilfield industry.

Permeability

The permeability was measured for some cooked geopolymeric compositions. The insulating ability of the cured geopolymer explored using systems that are kept for several days under high pressure and high temperature in the chambers with high pressure and the high temperature, to simulate conditions in oil wells.

Table 11 illustrates that geopolymer compositions described in this invention exhibit satisfactory permeability for use in the oilfield industry.

Table 11: water Permeability measured after curing at 90°C and 20.7 MPa (3000 psig)

Table 11
SampleA11B11C11D11
The permeability [MD]0,08<0,008<0,006<0,006

Sample A11 were made by dissolving the appropriate quantity of retarder setting in 265 g of water by addition of a mixture containing 232 g of metakaolin, 168 g of disilicate sodium and 414 g of silica as a filler to the solution with stirring by adding 13 g of sodium hydroxide under stirring API and pouring the suspension in the form in the chamber for curing for 7 days at 90°C and 3000 psi in accordance with the procedure API. The permeability of the sample A11 then measured for tsilindricheskoj the core (diameter of 1 inch and a length of 2 inches).

Sample B11 produced by adding a mixture containing 482 g standard fly ash type F and 96 g of disilicate sodium, 408 g of sodium hydroxide solution containing the accelerator, followed by stirring for API and pouring the suspension in the form in the chamber for curing for 21 days at 90°C and 3000 psi in accordance with the procedure API. The permeability of the sample B11 then measured for a cylindrical core (diameter of 1 inch and a length of 2 inches).

Sample C11 produced by adding a mixture containing 442 g standard fly ash type F and 88 g of disilicate sodium, 424 g of sodium hydroxide solution containing 3% by weight LiCl mixture, followed by stirring for API and pouring the suspension in the form in the chamber for curing for 21 days at 90°C and 3000 psi in accordance with the procedure API. The permeability of the sample C11 then measured for a cylindrical core (diameter of 1 inch and a length of 2 inches).

Sample D11 produced by adding a mixture containing 480 g of ultrafine fly ash type F and 96 g of disilicate sodium, 406 g of sodium hydroxide solution containing 7% by weight LiCl mixture, followed by stirring for API and pouring the suspension in the form in the chamber for curing for 21 days at 90°C and 3000 psi in accordance with the procedure API. The permeability of the sample D11 then measured for cylindricus the CSO core (diameter of 1 inch and a length of 2 inches).

Since the compositions of this invention exhibit satisfactory permeability, they can be used in the oilfield industry.

The use of geopolymer

Methods according to this invention is applicable to completion, such as, for example, oil and/or gas wells, water wells, geothermal wells, injection wells for steam injection into the reservoir, wells with directional air injection (Toe to Heel Air Injection - THAI), wells with sour gas wells for injection of carbon dioxide or wells and conventional wells. Accommodation geopolymeric composition in the well, subject to completion, completed by means that are well known in the field of cementing boreholes. Geopolymer composition is usually placed in the wellbore, a surrounding casing to prevent vertical connections through the annulus between the casing and the wellbore, or between a casing and the other casing larger in size. Geopolymer suspension is usually placed in the wellbore circulation of the suspension in the lower direction inside the casing with subsequent supply breakable cementing plugs and ashwathama the displacing fluid. Press CEMENTERIO the Naya tube usually shifts to the clutch and is placed near the bottom of the casing. Clutch grabs cementing plug to prevent preproduce geopolymeric compositions, as well as to minimize the number geopolymeric composition remaining in the casing. Suspension of geopolymer circulates upward through the annular space surrounding the casing in which it is left to cure. The annulus may be located between the casing and the other casing of larger size or may be located between the casing and the wellbore. As in the case of conventional cementing operations, such cementing using geopolymeric suspension may cover only a portion of the wellbore or, more typically, can be performed before the internal space of the next casing larger or sometimes up to the surface. This method is described for the completion of the cementing between the rock and the casing, but can be used with any type of completion, for example, shank, shank with a longitudinal slit apertures, a perforated tube, expanding the tube, permeable pipe and/or pipe system.

Similarly, the methods according to this invention is applicable to completion, such as, for example, oil and/or gas wells, water wells, geothermal squag the us, injection wells for steam injection into the reservoir, wells with sour gas wells for injection of carbon dioxide and conventional wells, in which allocation of geopolymeric composition in parts finishing well is performed by means well known in this technology cementing with reverse circulation.

Geopolymer composition can also be used for correctional cement under pressure and/or during maintenance. Geopolymeric material is forced through the perforations or slots in the casing regardless, formed these perforation holes or cracks intentionally or not, the breed and the well bore around the casing to be repaired. Geopolymeric material is thus to repair and seal badly insulated well, for example, when the initial cement or geopolymeric material is destroyed or not originally was posted in an acceptable manner, or when producing interval must be isolated.

Geopolymer composition can also be used if the well is abandoned and/or bridging. Geopolymeric material is used as the tube to partially or completely isolate the area well. Tube of geopolymer what about the material placed in the well by means well known in the field of cementing a well with a cementing plug.

Geopolymer composition can also be used when working with injection of cement mortar for the completion of part of the annulus, as described in Erik B. Nelson. Well Cementing. Geopolymeric material is used for completion of this annular space. The blank from geopolymeric material is placed within the well by means well known in the field of cementing wells.

Geopolymer composition can also be used to perform work requiring fast setting of the work performed in situ. Actually geopolitika the composition may have a well-controlled setting time, allowing immediate setting, if necessary. For example, to geopolymeric composition may be added to the combination retarder/accelerator, to provide a slower setting system for an extended period of time and then gripe when adding the accelerator.

Geopolymer composition can also be preserved by composition. As such, the suspension has a significant deceleration setting and remains deliberate manner in the liquid phase. Such suspension may be placed in the borehole and used if necessary.

In accordance with other variants of implementation of the data of the invention, methods of completion, described above, can be used in combination with conventional cement completion.

Examples Geopolymer composition

The examples below illustrate the practical use of this invention and the preferred options for its implementation.

Example 1

Geopolymer composition is made when the following quantities of components by weight of the total amount of dry ingredients: 58,1% of metakaolin and 41.9% of disilicate sodium. The dry ingredients are mixed with an appropriate amount of water, sodium hydroxide and additives. The density of the suspension is 1,53 g/cm3(12,80 lbs/gallon). Geopolymer has the following molar ratios of oxides:

SiO2/Al2O3=4,00

Na2O/SiO2=0,27

Na2O/Al2O3=1,07

H2O/Na2O=17,15

Example 2

Geopolymer composition is made when the following quantities of components by weight of the total amount of dry ingredients: 28.5% of metakaolin, 20,6% of disilicate sodium and 50.9% of the mixture of particles of silica. The dry ingredients are mixed with an appropriate amount of water, sodium hydroxide and additives. The density of the suspension is 1.84 g/cm3(15,40 lbs/gallon). Geopolymer matrix has the following molar ratios of oxides:

SiO2/Al2O3=4,00

Na2O/SiO2 =0,27

Na2O/Al2O3=1,07

H2O/Na2O=17,15

Example 3

Geopolymer composition is made when the following quantities of components by weight of the total amount of dry ingredients: 35,2% of metakaolin and 64.2% of disilicate potassium. The dry ingredients are mixed with an appropriate amount of water, potassium hydroxide and additives. The density of the suspension is 1.78 g/cm3(14,91 lbs/gallon). Geopolymer matrix has the following molar ratios of oxides:

SiO2/Al2O3=4,00

K2O/SiO2=0,27

K2O/Al2O3=1,07

H2O/K2O=17,46

Example 4

Geopolymer composition is made when the following quantities of components by weight of the total amount of dry ingredients: 83,3% standard fly ash type F and 16.7% of disilicate sodium. The dry ingredients are mixed with an appropriate amount of water, sodium hydroxide and additives. The density of the suspension of 1.66 g/cm3(13,83 lbs/gallon). Geopolymer has the following molar ratios of oxides:

SiO2/Al2O3=ceiling of 5.60

Na2O/SiO2=0,3

Na2O/Al2O3=1,08

H2O/Na2O=13,01

1. Suspension for use in oil and gas wells, comprising:
source aluminosilicate,
the carrier fluid,
the activator from the group, including the setup portion of the metal silicate, the metal aluminate, alkali activator, or combinations thereof,
the suspension is capable of pumping a composition with such a rheology that its viscosity is 300 SP or less, and the suspension can be cured under the conditions of the wells.

2. The suspension according to claim 1, also containing retarder setting, is able to regulate the times of thickening and/or stiffening of the suspension in terms of wells.

3. The suspension according to claim 1 or 2, in which the setting retarder selected from the group comprising boron-containing compound, lignosulfate, sodium gluconate, glucoheptonate sodium, tartaric acid and fosforsoderzhashchie compound or their mixture.

4. The suspension according to any one of claims 1 and 2, in which the setting retarder is effective in the temperature interval from 20 to 200°C.

5. The suspension according to any one of claims 1 and 2, also containing the accelerator, capable of regulating the times of thickening and/or stiffening of the suspension.

6. The suspension according to claim 5, in which the accelerator is a compound containing an alkaline metal.

7. The suspension according to claim 6, in which the accelerator is a compound of lithium or potassium.

8. The suspension according to any one of p and 7, in which the accelerator effective in the temperature range from 20 to 200°C.

9. The suspension according to any one of claims 1, 2, 6, or 7, also containing light particles selected from the group including cenospheres, ceramic, sodium-calc the th-borosilicate glass and aluminosilicate microspheres.

10. The suspension according to any one of claims 1, 2, 6, or 7, also containing hard particles selected from the group comprising manganese tetroxide, iron oxide (hematite), barium sulfate (barite), silica, and iron oxide/titanium (ilmenite).

11. The suspension according to any one of claims 1, 2, 6, or 7, also containing the gas phase.

12. The suspension according to claim 11, in which the gas phase is air or nitrogen.

13. The suspension according to claim 11, containing gas-forming additive, capable of formation of gas phase inside the suspension.

14. The suspension according to any one of claims 1, 2, 6, 7, 12 or 13, also containing phase is not miscible with water.

15. Suspension of 14, in which the phase is not miscible with water, is an oil phase.

16. The suspension according to any one of claims 1 to, 2, 6, 7, 12, 13 or 15, in which the density of the suspension varies between 1 and 2.5 g/cm3.

17. The suspension according to any one of claims 1 to, 2, 6, 7, 12, 13 or 15, also containing an additive selected from the group comprising non, antifoam, silica, additive for regulating water loss, additive to improve fluidity, a dispersant, a rheology modifier, a blowing agent, surfactant and additive preventing the deposition.

18. Suspension for use in oil and gas wells, comprising:
source aluminosilicate,
the carrier fluid,
the activator from the group comprising silicate m is metal, the metal aluminate, alkali activator, or combinations thereof, and
moderator setting, able to slow the thickening and/or stiffening the suspension, and/or accelerator capable of accelerating the thickening and/or stiffening the suspension,
in which the metal is an alkaline metal and the molar ratio of the oxides of M2O/SiO2is more than 0.20, while M is the specified metal,
the suspension is capable of pumping a composition with such a rheology that its viscosity is 300 SP or less, and the suspension can be cured under the conditions of the wells.

19. The suspension on p, in which the molar ratio of the oxides of M2O/SiO2is 0.25 or more.

20. The suspension according to any one of p and 19, in which the setting retarder is a boron-containing compound and the suspension specified geopolymeric composition has a molar ratio of oxides of B2O3/H2O less than 0.03.

21. The suspension according to claim 20, in which the molar ratio of the oxides of B2O3/H2O is 0.02 or less.

22. The suspension according to any one of p, 19 or 21, in which the atomic ratio of silicon to aluminum is in the range between 1.8 and 2.8.

23. Suspension under article 22, in which the atomic ratio of silicon and aluminum, usually equal to 2.

24. The suspension according to any one of p, 19, 21 or 23, in which the source of silicate in the bran from the group including fly ash type C fly ash type F, crushed blast furnace slag, clay, and partly of baked clay such as metakaolin), fine silica containing aluminium, natural aluminium silicate such as kaolin, synthetic aluminosilicate glass powder, zeolite, volcanic slag, allion, bentonite and pumice.

25. The suspension according to any one of p, 19, 21 or 23, in which the specified metal selected from the group comprising lithium, sodium, potassium, rubidium, and cesium.

26. The suspension according to any one of p, 19, 21 or 23, in which the alkaline activator is a hydroxide of an alkali metal.

27. The suspension according to any one of p, 19, 21 or 23, in which the alkaline activator and/or the carrier fluid encapsulated.

28. The suspension according to any one of p, 19, 21 or 23, in which the metal silicate and/or carrier fluid encapsulated.

29. The method of adjusting the density of the suspension for the oilfield industry, including the state provision of the said suspension in the carrier fluid by adding:
(i) light particles and/or heavy particles;
(ii) source of aluminosilicate;
(iii) activator from the group comprising a metal silicate, a metal aluminate, alkali activator, or combinations thereof.

30. The method according to clause 29, also comprising a stage of adding retarder setting, able to slow the thickening or stiffening of the suspension, and/or accelerator setting, able to accelerate the thickening and/or stiffening of the suspension.

31. The method according to clause 29 or 30, also comprising a stage of foaming suspension specified geopolymeric composition.

32. The method of adjusting the density of the suspension for the oilfield industry, including the following stages:
(i) provide such a suspension in the carrier fluid by mixing a source of silicate and an activator selected from the group comprising a metal silicate, a metal aluminate, alkali activator, or combinations thereof, and
(ii) foaming the specified suspension.

33. The method according to any of p, 30 or 32, in which the density varies in the range between 1 and 2.5 g/cm3.

34. The method of placing geopolymeric composition in a borehole in a formation, comprising the following stages:
(i) providing a suspension in the carrier fluid by mixing a source of silicate and an activator selected from the group comprising a metal silicate, a metal aluminate, alkali activator, or combinations thereof,
(ii) pumping the specified suspension in a borehole and
(iii) enabling the setting of the specified suspension in the well conditions and thereby forming geopolymeric composition.

35. The method according to clause 34, in which the stage of granting the suspension also contains the add is giving retarder setting, able to slow down the thickening and/or stiffening of the suspension.

36. The method according to clause 34 or 35, in which the stage of granting the suspension also contains the addition of the accelerator grip, is able to accelerate the thickening and/or stiffening of the suspension.

37. The method according to clause 34 or 35, including the stage of activation of the specified suspension in situ.

38. The method according to clause 34 or 35, in which stage of injection of the suspension is performed using conventional equipment for cementing wells.

39. The method according to clause 34 or 35, in which the method is used for placing geopolymeric composition in the annular space between the casing pipe and the wellbore.

40. The method according to clause 34 or 35, in which the method is used for placing geopolymeric composition through the hole made in the casing pipe.

41. The method according to clause 34 or 35, in which the method is used for placing geopolymeric songs to drown out the area well.

42. The method according to clause 34 or 35, in which the method is used for placing geopolymeric composition in order to seal the area well.

43. The method according to any of p, 30, 32, 34, or 35, in which the suspension is prepared in front stage injection and remains deliberate manner in the liquid phase, is capable of storing.



 

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FIELD: oil and gas production.

SUBSTANCE: procedure for restraint of water production in well consists in pumping solution of CL (cultural liquid) into insulated interval. Two equal portions are pumped. The first portion corresponds to solution of CL prepared on soft water of 1000 kg/m3 density at ratio 1:0.5-1, while the second one corresponds to solution prepared on reservoir mineralised water of density up to 1190 kg/m3 at ratio 1:0.3-0.5.

EFFECT: raised efficiency of repair-insulation operations due to creation of more resistant to water outbreak screen of water solutions of silicon-organic liquid - CL with controlled period of gelation excluding their preliminary hardening.

3 tbl

FIELD: oil and gas production.

SUBSTANCE: procedure consists in simultaneous effecting permeable walls of well borehole with scrapers for removal of filtration crust and with high-pressure jets generated from hydro-monitored heads of mud injector during well bottom hole deepening with drilling. Also, hydro-jets are directed at angle towards each other, they converge at one point on the wall of the well and destroy their nuclei, thus preventing destruction of walls of the well and formation of cavities. Well walls are subjected to the similar effect when the well is treated before lowering a producer for cementing. Drill agent containing dispersed solid particles is used as fluid for high-pressure hydraulic jets.

EFFECT: raised efficiency of mud fill, reduced expenditures for emergency-recovery operations and time for construction of well.

2 cl, 2 dwg

FIELD: oil and gas production.

SUBSTANCE: composition contains carbamide-formaldehyde resin, acid hardener and filler. As hardener there is used resorcin and ferro-chrome-lignosulphonate, and as filler there is used carbon white CW-120 or talk, or rubber powder, or chalk at the following ratio of components, in weight shares: carbamide-formaldehyde resin 100; resorcin 7-15, ferro-chrome-lignosulphonate - FCLS-M 1.5-25, filler 3-8.

EFFECT: reduced water loss of backfilling solution and increased strength and adhesion characteristics of cured composition.

2 cl, 1 tbl, 20 ex

FIELD: oil and gas production.

SUBSTANCE: composition includes phenol-formaldehyde resin of resol type, curing agent and mineral or organic filler. Additionally composition contains an activating agent of the process - resorcin and expanding additive EA-100. As ageing agent there is used ferro-chrom-lignosulphonate FCLS-M and additionally expanding additive of type AE-100 at the following ratio of components, wt shares: phenol-formaldehyde resin PFR-3027B 100; ferro-chrom-lignosulphate FCLS-M 1.0-10; resorcin 1.5-10; filler (carbon white CW-120 or talk, or rubber powder, or chalk or barite) 4-8; expanding additive EA 5-15.

EFFECT: reduced water loss of backfilling solution and increased strength and adhesion characteristics of cured composition.

2 cl, 3 tbl, 11 ex

FIELD: oil and gas industry.

SUBSTANCE: in manufacturing method of siliceous proppant, which involves charge grinding, granulation and baking of granules, natural highly siliceous sand or its mixture with quartzite in quantity of 1-25% of mass of mixture at SiO2 content in the charge of not less than 87 wt % is used as charge; grinding is performed to the size of not more than 10 mcm at fraction content of not more than 5 mcm, which is not less than 50 wt %, and calcination - at 1120-1300°C at heating rate of 1000-2500°C/h and cooling rate of 1000-2000°C/h. Siliceous proppant is characterised by the fact that it has been obtained by means of the above method; at that, content of christobalite in calcined granules does not exceed 10 vol %.

EFFECT: decreasing proppant density at maintaining allowable strength values of granules.

3 cl, 2 ex, 1 tbl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention refers to sealing compositions for insulation works carried out in production wells of minefields and underground storage of gas, which can be used for insulation of between-casing and after-casing space, repeated sealing of threaded connections of casing strings. Sealing composition for insulation work in the well includes the following, wt %: synthetic camphor 1-49, polyvinylbutyral film 1-6, isopropyl alcohol is the rest.

EFFECT: increasing efficiency of insulation works carried out in wells owing to using sealing composition with improved process properties determined with increased plasticising properties, adhesion of composition to surfaces of protective and production strings, and increasing the time of the well operation between overhauls.

1 tbl, 5 ex

FIELD: oil and gas industry.

SUBSTANCE: drilling fluid on hydrocarbon basis includes the following, wt %: liquid paraffin C7-C22 52.7-56, organophilic clay powder 2.5-4.7, water 1.5-9.5, sodium formate or sodium acetate 1.5-4.7, asphalt mastic 5.6-7.9, glycerine ether of tall colophony 1.5-7.1, neutraliser of hydrogen sulphide 0.1-0.3, non-hydrophobisated weighting agent in quantity providing the specified density of the fluid. Non-hydrophobisated disperse chalk or barite is used as weighting agent.

EFFECT: maintaining rheologic and filtration parameters of drilling fluid at the required level.

2 cl, 4 tbl

FIELD: oil and gas industry.

SUBSTANCE: drilling fluid on synthetic basis includes the following, wt %: water 20.3-47.3, polyatomic alcohol 20.3-47.3, biopolymer 0.23-0.34, sodium formate or sodium acetate 20.3-27.0, anionic emulsion ROSFLOK PV 3.4-6.8, bactericide 0.07-0.14, disperse chalk 1.7-5. Drilling fluid is prepared by introduction of biopolymer to water at constant mixing; polyatomic alcohol is added to the formed structured liquid in portions after dilution; after that, anionic emulsion is added; in order to control polarity of drilling fluid components and increase its heat resistance, there added is salt-electrolyte; in order to prevent biological decomposition of biopolymer, the latter is treated with bactericide; weighting-up of the fluid is performed with disperse chalk; drilling fluid is obtained at mixing with blade agitator with speed of 5000 rpm.

EFFECT: maintaining rheologic and filtration parameters of the fluid.

3 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: liquid composition contains the following: suspension on oil basis, which includes base oil, organophilic clay, polar activating agent, wetting agent, and composition improving the operability in winter conditions, which contains one or many composite monoesters of polyols and/or composite diesters of polyols. Composition is meant for hydraulic fracturing of underground formation, removal of combined wafer from productive underground formation. Hydraulic fracturing method of underground formation involves pumping to the formation under the pressure which is enough for fracturing, liquid for fracturing, which contains propping agent and suspension on oil base, which includes base oil, organophilic clay, polar activating agent, wetting agent and the above composition, or according to the other version - fracturing liquid containing the above suspension, and pumping to the formation subjected to fracturing under pressure which is enough for protection of cracks against joining of carrying liquid with propping agent. Production method involves circulation and/or pumping to production well of the liquid including the above suspension.

EFFECT: improving operability in winter conditions.

25 cl, 18 tbl, 3 ex, 4 dwg

FIELD: oil and gas industry.

SUBSTANCE: thermoplastic solid-fuel composition containing ammonium nitrate, rubber, combustion catalyst includes powder-like butadiene-nitrile rubber with particle size of 0.4-2.0 mm as rubber, potassium bichromate or ammonium bichromate as combustion catalyst at the following component ratio, wt %: ammonium nitrate 79 - 88, the above rubber 8-18, potassium bichromate or ammonium bichromate 1-11.

EFFECT: increasing rate of combustion of the composition at increased pressure and reducing the content of solid combustion products.

4 ex, 1 tbl

FIELD: oil and gas industry.

SUBSTANCE: plugging composition for insulation of lost-circulation zones includes the following, wt %: Portland cement 50-50.3, expansion agent - copolymer of carboxylic acids of acrylic row, their esters and salts 1-1.1, hardening accelerating agent - calcium chloride 2.4-2.6, water 37 and water-repellent admixture - silicone fluid on the basis of sodium methylsiliconate 9.3.

EFFECT: improving colmatation ability of plugging composition at elimination of absorptions of various intensity from partial to complete ones.

1 tbl

FIELD: oil and gas industry.

SUBSTANCE: methods involving the use of composition for slow increase in adhesive ability, which includes water agent for increasing the adhesive ability and activating agent of slow separation of the acid which is used for stabilisation of particles and minimisation of particle migration inside underground formation. Invention has been developed in dependent claims.

EFFECT: improvement of operating flexibility and controllability of operations and mechanical elasticity of stabilised masses.

20 cl, 1 ex

FIELD: oil and gas industry.

SUBSTANCE: method for obtaining reagent for drilling fluid involves treatment of lignosulphonate with sulphuric acid and bichromate of alkali metal to pH 1-1.5 with further partial neutralisation by means of sodium hydroxide to pH 4-5; drying. At the specified treatment there introduced is sulphide-alkali drain - waste of petrochemical activities, which contains 6-8 g/l of sulphide sulphur, in quantity of 25-30 parts by weight.

EFFECT: reducing the contamination of waste water with connections of hexatomic chrome.

1 tbl

FIELD: chemistry.

SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.

EFFECT: invention increases stability of the formed protective paint coating to thermal-oxidative reactions, improves environmental safety, fire-resistance of the protective coating and endows said coating with bactericidal properties.

7 cl, 2 dwg, 1 tbl

FIELD: production and exploratory well drilling, particularly foaming drilling fluids used during penetration through incompetent rock intervals and during primary productive oil and gas deposit opening in the case of abnormally low formation pressure.

SUBSTANCE: foam composition comprises surfactant, foam stabilizer, water, water hardness control additive and lubricant. The water hardness control additive is sodium silicate. The lubricant is VNIINP-117 emulsion. The foam stabilizer is polyacrylamide, the surfactant is sulphonole. All above components are taken in the following amounts (% by weight): sulphonole - 0.8-1.5, sodium silicate - 0.2-0.5, polyacrylamide - 0.1-0.5, VNIINP-117 - 0.5-2, remainder is water.

EFFECT: reduced power inputs for well drilling, as well as reduced coefficient of friction between drilling tool and well wall.

1 tbl

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