Free flowing coating particles, production method and use thereof

FIELD: chemistry.

SUBSTANCE: free flowing coated particles, having size ranging from 6 mesh to 200 mesh, where each particles has a substrate and a coating on the substrate. Said coating contains a continuous phase which contains a curable resol phenol-formaldehyde resin, and reactive powdered particles embedded into the continuous phase or adhered to said phase, wherein the powdered particles contain at least one component selected from a group consisting of resol phenol-formaldehyde resin, phenol-formaldehyde novolac resin, ester, an acrylic compound and urethane. The method of producing said particles involves the following steps: mixing a substrate with a liquid coating material from the curable resol phenol-formaldehyde resin at temperature ranging from approximately 10°C to approximately 65°C to form a resin curable coating in form of a continuous phase on the substrate; mixing the reactive powdered particles with the resin-coated substrate to embed said particles into the continuous phase of the resin coating or adhere said particles to the substrate.

EFFECT: possibility of cost-effective production of highly effective particles in industrial conditions.

43 cl, 4 tbl, 5 ex, 10 dwg

 

Data related to the application

This application claims priority from application U.S. serial number 11/726573, registered on March 22, 2007, the entire contents of which is thus incorporated into the present application as reference material.

The technical field to which the invention relates.

The present disclosure relates to coated particles and the method of their production and application. In particular, the disclosure relates to coated particles, which are used as proppants (riving fillers) or in gravel packing and manufacture by coating particles of a liquid phenol-formaldehyde audio record at room temperature, causing the powder, for example, Novolac powder or rezol powder, the coated particle, followed by stirring until dry at low temperature. If desired, the particles can be used in applications covered by sand in the foundry industry.

The prior art to which the invention relates.

The term "proppant" refers to the granular material, which is injected into the cracks of subterranean formations surrounding oil wells, gas wells, water wells and other similar wells have been drilled with the purpose of providing support (backup)to keep the cracks open and allow gas or liquid prot is to look through the crack to the well or reservoir. The proppants are typically used to prop open fractures formed in the subterranean formations, such as oil and natural gas wells, as the result of hydraulic fracturing.

Uncoated and/or coated particles are often used as proppants for the preservation of open cracks when conducting hydraulic fracturing in a subterranean formation, for example in oil - or gas-bearing strata, or as gravel packing.

Uncoated proppants are typically particles of sand, ceramics, glass, beads, walnut shells, and others known in the art particles. Used for backup cracks particles usually contain sand and sintered ceramic particles. The advantage of sand is its cheapness. The drawbacks are its relatively low strength (high razdavlivanii) and lower fluidity than that of sintered ceramic particles. Sintered ceramic particles are also used as proppants. The disadvantage of ceramic particles is that the sintering is carried out at high temperatures, which leads to high energy costs and this uses expensive raw materials.

Coated proppants are individual particles, coated with resin. Individual particles, as a rule, are particles of sand, KERS is key, glass beads, shell walnuts and others known in the art particles. Coating proppants can be pre-solidified or are cured. Pre-caulk proppants include epigastric core and a coating of resin, utverzhdenii prior to entering into the underground reservoir. Curing the proppants include epigastric core and a coating of resin, curing in the well with the formation of the hardened packing proppant. Usually used for curing on the substrate proppants (sand, ceramics and so on) of the resin compositions into longevity highly crosslinked coating on the surface of the substrate.

Covered with curable resin proppants and proppant coated with utverzhdenii resins are commercially available for use as proppants. Curable proppant has a resin coating comprising a resin, which is typically at least partially, but not fully overiden. "Pre-cured" proppant, by contrast, has utverjdenie resin coating. The expression "cured" and "curing" are defined for the present description using three tests, which are traditionally used in the technique.

a) Test temperature adhesion: the coated material is placed on the hot bar to determine the melting temperature and determine n is inissue temperature, when the coated material sticks to the blade to determine the melting temperature. "Temperature adhesion above 175°C usually indicates the cured material, which depends on the resin system.

b) Test by extraction with acetone: described below is the method of extraction with acetone to dissolve the fraction of the resin in the coating, which has not been cured.

c) Test the tensile strength of compression: no adhesion or no adhesion between particles coated after wet compression at 70 kg/cm2and 93°C for up to 24 hours usually indicates the cured material.

However, unless otherwise specified, the expression cured and cured determined using a test with extraction with acetone.

The proppants are typically used to enhance the production of oil and/or gas by providing in the formation of the channel conductivity. Rupture of an underground reservoir is produced with the aim of increasing the production of oil and/or gas. The gap is carried out, pumping viscous breaking the fluid or foam under high pressure ("pressure") into a well to crack formation. A similar effect can be achieved by pumping a thick fluid (water with a low concentration of polymer) with a high rate of discharge. Once a crack forms in the reservoir is placed granular material is, called "propping agent" or "proppant"to maintain the fracture in a propped condition after a reset discharge pressure. As crack formation, the proppant is slid into the crack, suspending them in a more fluid or foam to fill the cracks with a slurry of proppant in the fluid or foam. Dropping pressure proppants form the gasket, which serves to keep the cracks open. Backed by a crack provides, therefore, in the layer of high-conductivity channel. The degree of stimulation, which gives the hydraulic fracturing operation largely depends on the parameters, the conductivity of the crack length backed cracks, height backed cracks and backed by the width of the crack.

The operation of stuffing a gravel used to reduce migration nestsementirovannyh Sands/fines in the wellbore. Operations gaskets gravel suspended in a carrier fluid is coated and/or uncoated particles into the wellbore where it should be placed gravel packing. The carrier fluid vysajivaetsya in the subterranean zone and/or returned to the surface, while the particles remain in the annular space between the operating string and the casing or outside of the casing in the underground area adjacent to the shaft SC is ageny.

The operation of stuffing a gravel include the location of the screen for gravel packing the well bore and packing the annular space between the screen and the wellbore particles. Screen gravel packing usually refers to the type of filtration units are used to support and retain particles that are placed during the operation of filling with gravel. Available in a wide range of sizes and configurations of screens to match the characteristics of a particular wellbore, the extracted fluid and sand underground reservoir. Such gravel packing can be used for stabilization of the reservoir, causing minimal impact on well productivity. Gravel packing acts as a filter to separate the reservoir sand from the produced fluids, leaving at the same time, the possibility of the produced oil and/or gas to flow into the well. The effect of the particles is to prevent the blockage of the reservoir Sands of the screen or migrating with the produced fluids, and the role of the screen is to prevent the escape of fines to the surface and out of the well.

Gravel packing may also be used to protect the continuity of the production borehole walls by the use of a tightly Packed layer of aggregate containing sand, gravel, or both between the borehole wall and operating the column, saving time and costs for installation of steel casing from the surface to a productive zone, which may be at a distance of many thousands of feet below the surface. Gravel packing is inherently permeable to the target hydrocarbon fluid and provides structural reinforcing the walls of the well bore against internal collapse or disrupting the flow. Such systems exploration wells are called completions "uncased wellbore". Apparatus and method by which a cushioning layer of gravel is placed between the wall of the wellbore and the production column, common name: the system for gravel packing an uncased wellbore. Unfortunately, the system for gravel packing an uncased wellbore current level of technology used for space and packing gravel along the zone of production of hydrocarbons, subject to significant risk of accelerating collapse of the borehole wall due to fluctuations downhole pressure along the production zone. These pressure fluctuations are the cause superficial manipulation of downhole tools with direct circulation of the fluid inside the borehole and the mounting column. Additional discussion gravel packing is provided in U.S. patent No. 6382319 included in the present application as reference material.

In kotoryj situations, the processes of hydraulic fracturing and gravel packing are combined into a single operation, achieving stimulated production of gravel and ring gaskets to reduce the outflow of reservoir Sands. These transactions are often referred to as operations explosive gaskets". In some cases, the operations are completed installation in place of the display unit, while the environment for hydraulic fracturing is pumped through the annular space between the casing and screen. In such situation, the hydraulic fracturing operation normally ends with a state of screenout (zastopowania receiving environment for hydraulic fracturing), resulting in between the screen and the casing is formed an annular gravel packing. It is possible to combine the operation of hydraulic fracturing and packing gravel in a single operation.

In addition, when extracting the hydrocarbons of the type of natural gas and crude oil from subsurface strata of the earth through wells drilled in uglevodorodnom productive areas, another noteworthy issue is the prevention of the inflow into the well of sand. Oil, gas and water from unconsolidated or poorly consolidated formations usually accompanied by the introduction into the well with the produced fluids particle formation Sands. Getting into the borehole together with downhole fluids sand poses serious problems, such as therefore is the use of subsurface and surface production equipment, as well as the accumulation of sand in the wellbore and surface separators. For many years, with varying degrees of success using several methods, such as gravel packing, screens and consolidation with plastics. However, these methods have several technical and cost limitations. Further discussion of preventing ingress of sand is given in U.S. patent No. 6364019 fully incorporated into the present application as reference material.

When in the oil industry are faults uglevodorodnom layers, the application in practice of proppants to save a large surface area created by using the gap becomes normal. It is highly desirable that the particles of proppant were efficient and could be made using a highly efficient way (that would be economically attractive). In addition, it would be desirable to develop coated particles that could be produced in remote areas, such as fisheries, located on or close to the location of the well.

Disclosure of inventions

The present invention relates to engineering of coated particles with a range of particle size from about 6 mesh to about 200 mesh (3360-74 µm) and each particle contains:

a substrate selected from the group consisting of

h is sticy of the substrate containing inorganic material and, optionally, at least partially utverjdenie floor,

particle-substrate containing an organic material and, optionally, at least partially utverjdenie floor,

composite particles containing a substantially homogeneous molded part containing the first portion of binder, and filler particles dispersed throughout the mentioned first portion of a binder where the specified first portion at least partially overiden and where the size of the filler particles ranges from about 0.5 to about 60 μm, and

hybrid particle containing composition layer, located on the inorganic core particle, and a composite layer contains at least partially utverjdenie organic coating and filler particles, and the size of the filler particles ranges from about 0.5 to about 60 μm and

the coating on the substrate, and the coating contains a continuous phase containing curable rezol phenol-formaldehyde resin containing reactive and directionspanel powder particles embedded in or adhering to the continuous phase, where the powder particles contain at least one member from the group consisting of phenol-formaldehyde resin,phenol-formaldehyde Novolac resin, of ester, acrylic compounds and urethane.

As for the method of the invention the present invention relates to a method for preparing engineering of coated particles with a range of particle size from about 6 mesh to about 200 mesh (3360-74 µm)containing the substrate and on the substrate coating, and the coating contains a continuous phase containing a curable liquid rezol phenol-formaldehyde resin containing powder particles embedded in or adhering to the continuous phase, and reactive powder particles contain at least one member from the group consisting of phenol-formaldehyde resin, phenol-formaldehyde Novolac resin of ester, acrylic compounds and urethane, which includes stages:

mixing at a temperature from about 10°to about 65°With the substrate with a liquid coating material with the formation of the resin cured coatings in the form of continuous phase on a substrate,

where the substrate is selected from the group consisting of

particle - substrate containing an inorganic material and, optionally, at least partially utverjdenie resin coating,

particle - substrate containing an organic material and, optionally, at least partially utverjdenie resin coating,

composite particles containing) the governmental degree homogeneous molded particle, containing the first portion of binder, and filler particles dispersed throughout the mentioned first portion of a binder where the specified first portion at least partially overiden and where the size of the filler particles ranges from about 0.5 to about 60 μm and

hybrid particle containing composition layer, located on the inorganic core particle, and a composite layer contains at least partially utverjdenie organic coating and filler particles, and the size of the filler particles ranges from about 0.5 to about 60 μm; and

where the coating material includes curing rezol phenol-formaldehyde resin;

contact powder coated particles to a resin substrate with the aim to implement it in or glued to the resin coating in a continuous phase.

Used in the way that the particles can be reactive or directionspanel.

Reactive powder particles in the product and/or method which are reactive to at least above the continuous phase. The use of reactive powders best way improves the characteristics of unlimited limit of the compressive strength (UCS) of the particle. Directionspanel particles, such as quartz flour, are inert in Rel is the solution to the continuous phase.

Typically, the reactive powder particles contain at least one member from the group consisting of rezol phenol-formaldehyde resin, phenol-formaldehyde Novolac resin of ester, acrylic compounds, and urethane. In this method of cooking used low-temperature deposition of organic resin on the sand and ceramic substrates in cycles, occupying just minutes as a result of which receive high-performance coated particles for oil (and gas) industry. The powder added with the aim of effectively drying the applied liquid coating and allow the coated particles to be separated and to be engineering.

The substrate is defined as the part of the particles is covered by one or more outer coatings of the present invention. The substrate may be present in the coated particles in an amount of from about 85 to approximately 99.5 wt.% calculated on the total weight of coated particles. In one of the embodiments in which the outer coating is placed directly on the sand or ceramic particles, the substrate is present in an amount of from about 95 to approximately 99.5 wt.% calculated on the total weight of coated particles.

External resin coating is usually from 0.5 to 15% by weight of the particles.

In one embodiment, the implementation of the external coating p is meshaut directly on a single inorganic particle. Typically, the particle-substrate containing inorganic material is a sand or ceramic particle-substrate. Preferred inorganic substrate is sand 40/70. In embodiments, the implementation uses inorganic particle-substrate, is covered by one or more layers of coating, containing a continuous phase containing rezol phenol-formaldehyde resin and a reactive powder particles. Dry engineering particle is predominantly characterised by weight loss on ignition (LOI) from about 0.3 to about 8, from about 0.3 to about 5, from about 0.5 to about 5, or from about 0.75 to about 4. Unless otherwise noted, all percentages disclosed herein, are given in weight percent.

In the variants of implementation, which uses organic particle-substrate, dried engineering particle is predominantly characterised LOI from about 0.3 to about 5%, not including LOI, which can be attributed to the annealing of organic particles of the substrate.

In embodiments, the implementation of the coated particles in which the substrate is a composite particle, the LOI is probably a combination of LOI composite substrate (which is typically 12 to 15% of the total weight of the substrate after curing) and LOI of the resin coating on the substrate (the t 0.5 to 5% of the total weight of the coated particles). In such scenarios, the implementation of the LOI is typically from about 12 to about 20% (including LOI, which can be attributed to the organic binder of the composite substrate and the coating, but not including LOI (if any), which may be attributed to the filler composition of the substrate). Typically, the composite substrate is from about 95 to approximately 99.5 wt.% coated particles of the present invention.

The composite substrate may contain from about 10 to about 90 wt.% and usually from about 70 to about 90 wt.% inorganic filling material calculated on the total weight of the composite substrate. In one embodiment, the implementation of the inorganic materials may be present in an amount of from about 20 to about 80 wt.% calculated on the total weight of the composite substrate. In another embodiment, the inorganic materials may be present in an amount of from about 30 to about 70 wt.% calculated on the total weight of the composite substrate. In one inorganic materials may be present in an amount of from about 40 to about 60 wt.% calculated on the total weight of the composite substrate.

Typically, the composite particle has a sphericity of not less than about 0.7.

In embodiments, the implementation of the coated particles in which the substrate is a hybrid h is itzá (inorganic core particle, having a composite layer of organic coatings and inorganic filler), and in this case, the LOI should be a combination of LOI composite substrate (which is usually from 5 to 20% of the total weight of the substrate after curing) and LOI of the resin coating on the substrate (from 0.5 to 5% of the total weight of the coated particles). In such scenarios, the implementation of the LOI is usually from about 5.5 to about 25% (including LOI, which can be attributed to the organic binder of the hybrid substrate and coating). Typically cured or at least partially cured composition layer is from about 25 to about 40 wt.% hybrid particles. Typically, the hybrid particle is from about 95 to about 99 wt.% coated particles of the present invention.

The ratio of the components, the order of additions and added and the mixture is chosen such that formed above engineering particles. For example, if the powder is mixed with inorganic particles uncoated substrate before applying the liquid audio record, adequate cover is not formed. The ratio rezol liquid and powder are also selected so to get the desired coverage. Too much powder leads to excess loose powder, and too much liquid audio record tighten the drying and/and and promotes agglomeration of the particles (many stuck with one another particle).

The present invention relates to a method of forming the proppant packing or gravel packing, including the suspension described above engineering particles in the carrier fluid with the formation of the slurry and pumping the slurry into an underground reservoir.

The present invention relates also to the particle proppant or gravel, containing a substrate having a coating of rezol resin containing powder embedded in the floor of rezol resin.

The coated sand or ceramic substrates of the liquid phenol-formaldehyde audio record at room temperature followed by the introduction of powdered phenol-formaldehyde Novolac resin (with or without corrective additives such as hexamethylenetetramine) provides high-performance engineering is covered with the resin particle, which can be used as oil proppant.

A coating of liquid resin is reactive toward the reactive powder. For example, rezol floor can contribute to curing Novolac powder and/or powder may contain hexamethylenetetramine (NEH) to enhance curing rezol coverage. Typically, reactive powder or directionspanel powder has an average particle size of about 200 mesh (74 μm) or less, or about 230 mesh (63 μm) elemense, or about 270 mesh (53 μm) or less. For example, a typical particle size of the powdered resin is in the range from 15 to 35 μm with a small amount of fines. Reactive powder mainly contains Novolac powder or rezol powder. Typically, at least a large part of the powder in or on the coating contains a reactive resin powder. Directionspanel powders and reactive powders do not dissolve or do not dissolve to an appreciable extent in water technical liquids or oil-based liquids.

In the external-curable coating typical ratio of liquid rezol resin to the powder (total reactive powder and possible inorganic powder) is approximately 1:3. The ratio by weight of liquid audio record to the powder coating is mainly 20-30% liquid audio record 70-80% of the powder. When applying to the substrate a certain amount of liquid audio record evaporates, as a result we have 15-20% of the dry material from the original audio record 80-85% of the dry material from a powder. Thus, for example, particles having inorganic particle-substrate and LOI of about 3 wt.%, the total amount of powder in the final part will be 80-85%×3%=2.4 to 2.5 wt.%. The ratio of liquid to powder may vary depending on the surface area of the coated particles and the reaction conditions. These conditions and the weight ratio is determined so that the resulting particles were dried and engineering with a small amount or, in the absence of free excess powder.

Cured coatings can be applied at the site of the well or close to it. However, the present invention applies to the manufacture of coated particles, which are pre-covered with obtaining proppant or installation of the coating on the sand or in various remote locations, such that form part of transshipment-inventory warehouse, on site wells or near it. The way that this rapid and economical, allowing rapid deployment of production capacities at low capital cost.

The advantage of the method of the present invention is that it allows to obtain a cured coated particle that sticks to the wellbore. Thus the present method can be carried out in remote locations for inexpensive installation. You can also save on transportation costs, minimizing the costs associated with the transportation of the substrate. Moreover, this method is swing (or with slight heating), but because it is more economical in comparison with the similar ways in which phenol resin is heated is, to apply the coating to the substrate, or which use heat for drying or curing of the resin coating. Avoid heat, this method also minimizes the emission of volatile substances, than forced to meet in the process in which phenol resin is heated to apply the coating to the substrate, or which use heat for drying or curing of the resin coating.

Brief description of drawings

The following is a brief description of the drawings in which the same numbers indicate the same elements.

Figure 1 is an example implementation of the covered particles containing inorganic solid or solid organic substrate on which is rezol a coating that contains a reactive powder.

2 - another option is the implementation of the coated particles, which comprises a solid inorganic substrate on which is solid rezol a coating that contains a Novolac or rezol powder and inorganic or inert organic fillers.

Figure 3 is another variant of implementation of the coated particles, which contains the substrate, where the substrate contains a composite particle, which is an agglomerate of inorganic particles and a binder, on which is a coating that contains reactive is Orasac.

Figure 4 is another variant implementation of the coated particles, which contains the substrate, where the substrate contains a hybrid particle containing composition layer, located on the inorganic core particle, and a composite layer contains utverjdenie organic coating and the inorganic filler, which is rezol a coating that contains a reactive powder.

5 is a photograph of particles freshly prepared in the laboratory sample And at magnification of about 10X.

6 is a photograph of particles freshly prepared in the laboratory sample at magnification of about 10X.

7 is a photograph of the core of the particles of the sample after the test in compression at 8,45 MPa and 93°C at a magnification of about 10X.

Fig - photography particles of the sample after the test, the hot tensile test at a magnification of about 10X.

Figure 9 - sample neozidannoe powder audio record from one of the comparative examples, the increase of approximately 12X.

Figure 10 - sample of the product obtained by the method with reversed order of the coating and the sample of powder from one of the comparative examples, the increase of approximately 30X.

A detailed description of the preferred embodiments

In accordance with the concepts of the present application, the terms "first", "second", etc. do not denote any order or C is aImost, and tend to be used to distinguish one element from another, and definite and indefinite articles do not imply limitation of quantity, but rather denote the presence of at least one of the mentioned positions. In addition, given in the application ranges include the endpoints and is suitable for combining independent.

Used particles of proppant or gravel packing containing substrate particles having a coating of rezol resin containing reactive powder, such as Novolac or rezol powder embedded in the floor of rezol resin.

Generally, the proppant, gravel packing or foundry sand individual particles of the granular substrate have a size in the range of rooms sit according to USA Standard Testing (standard test USA) from about 6 to 200 mesh, for example from 20 to 40 mesh. Usually the individual particles of the granular substrate proppant or gravel gaskets have a size in the range of rooms sit according to USA Standard Testing from about 8 to about 100 mesh (i.e., the grid apertures from about 0,238 to about 0.015 g cm), from 20 to 80 mesh or predominantly from 40 to 70 mesh. Typical individual particles of the granular substrate have a diameter of from about 0,0254 to 0,1016 see generally, in the case of foundry sand substrate is a sand or ceramics.

For example, under the key 2, 21, 42 figure 1-4 may have an average particle size from about 100 to about 1400 μm (from about 140 mesh to about 14 mesh), or from about 300 to about 600 μm (from about 50 mesh to about 30 mesh), or from about 400 to about 500 μm (from about 40 mesh to about 35 mesh).

Before use as proppant or gravel packing on the substrate of the organic coating is cured.

Figure 1 shows a typical implementation of the coated particles 10, which includes the particle-substrate 2, on which is organic coating 4. Particle-substrate 2 may contain organic material and/or inorganic material. Particle-substrate 2 mainly represents a single inorganic particle. Organic coating 4 contains curable rezol polymer in a continuous phase 6 and reactive powder 8 embedded in or adhered to the continuous phase 6. If desired, together with reactive powder 8 or may be used instead of directionspanel powder, such as particles of an inert inorganic or inert organic filler. Preferred reactive powders, as they can best way to improve an unlimited limit of the compressive strength of the particles 10.

Figure 2 shows a coated particle 12, redstavlyaya a variant implementation of figure 1, modified additional inclusion particles 14 inert organic or inert inorganic filler embedded in or adhering to continuous rezol phase 6.

Figure 3 shows another variant of implementation of the covered particles 20, which includes a substrate 21 and the cover 4 on the substrate 21. The substrate 21 includes a sinter the inorganic particles 22 and the junction 24. Floor 4 contains reactive powder 8 and the continuous rezol phase 6. If desired, together with reactive powder 8 or may be used instead of directionspanel powder, such as particles of an inert inorganic or inert organic filler, such as silica flour. Reactive powders can be a successful way to improve the unlimited limit the compressive strength of the particles 20.

Figure 4 shows another typical implementation, including particle 40, which includes a substrate 42 having the inorganic particle 44 as a core and at least partially utverjdenie coating 46, which contains inorganic or organic fillers 48. On the specified substrate 42 of the coating 52. The cover 52 includes a continuous phase 54 cured of audio record and reactive resin powder 56. If desired, together with reactive Orascom or may be used instead of directionspanel powder, such as particles of an inert inorganic or inert organic filler, such as silica flour. Reactive powders can be a successful way to improve the unlimited limit the compressive strength of the particles 40. Preferably, the powder 56 contained reactive novolak or audio record. If desired, the coating 52 or it can be placed directionspanel powders (not shown), such as quartz flour. Typically, at least the main part of the powder in or on the coating 52 contains a reactive resin powder.

A. Single particle-substrate

How, for example, from figure 1 and 2, the substrate can be a single particle. The substrate can be any organic or inorganic solid granular materials commonly used as propping agents, gravel packing, or to prevent admission into the well of sand. Suitable granular materials include, for example, sand, natural mineral fibers, such as zircon and mullite, ceramics such as sintered bauxite or sintered alumina, ceramidase refractories, such as milled glass beads and walnut shells. The substrate can have any desired shape, such as spherical, egg-shaped, cubic, polygonal, etc. it is Normally desirable that ponticiello spherical shape. The substrate can be porous or non-porous. The substrate does not melt at temperatures below 93 or 107°C and, as a rule, they do not melt at temperatures below 230 or 290°C. the substrate Particles are rigid and resistant to deformation, or they can be deformable. In some cases, a single particle-substrate may be at least partially utverjdenie resin coating.

The publication of the patent application U.S. No. 2006/0078682 in the name of McDaniel et al., fully incorporated into the present application as reference material, also revealed particles of the substrate containing silica and alumina in the weight ratio of silica to alumina from about 2.2 to about 5, and with a bulk density less than or equal to 1 g/cm3that are suitable for use as a single particle-substrate in the present invention.

Examples of other inorganic materials that can be used in the substrate are inorganic oxides, inorganic carbides, inorganic nitrides, inorganic hydroxides, inorganic oxides with hydroxide coatings, inorganic carbonitrides, inorganic oxynitride, inorganic borides, inorganic borocarbide, etc. or a combination containing at least one of the above inorganic materials. Examples of qualifying the inorganic materials are metal oxides, metal carbides, metal nitrides, metal hydroxides, metal oxides with hydroxide coatings, carbonitrides of metals, oxynitride metals, borides of metals borocarbide metals, etc. or a combination containing at least one of the above inorganic materials. The metal cations used in the above-mentioned inorganic materials can be selected from transition metals, alkali metals, alkaline earth metals, rare earth metals, etc. or combinations containing at least one of the above metals.

Examples of suitable inorganic oxides include silica (SiO2), alumina (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), cerium oxide (CeO2), manganese oxide (MnO2), zinc oxide (ZnO), iron oxides (for example, FeO, α-Fe2O3, β-Fe2O3, Fe3O4and the like), calcium oxide (Cao), manganese dioxide (MnO2and Mn3O4), or a combination containing at least one of the above inorganic oxides. Examples of suitable inorganic carbides include silicon carbide (SiC), titanium carbide (TiC), tantalum carbide (TAC), tungsten carbide (WC), hafnium carbide (HfC), etc. or a combination containing at least one of the above carbides. Examples of suitable nitrides include NITR the waters silicon (Si 3N4), titanium nitride (TiN), etc. or a combination containing at least one of these nitrides. Examples of suitable borides are bored lanthanum (LaB6), chromium borides (CrB and CrB2), borides of molybdenum (MoB2Mo2B5and MoB), bored tungsten (W2B5), etc. or a combination containing at least one of these borides. Typical inorganic substrates are those which contain silica and/or alumina.

Other examples of inorganic materials that can be used in the substrate are silica (sand), isinit (rare earth yttrium-iron-titanium-niobium oxide-hydroxide), anatase (titanium oxide), bindheimite (lead-antimony oxide hydroxide), bixbyite (manganese-iron oxide), brookite (titanium oxide), chrysoberyl (beryllium-aluminum oxide), columbite (iron-manganese-Nabieva-tantalum oxide), corundum (aluminum oxide), cuprite (copper oxide), euxenite (rare earth-yttrium-Nabieva-santalova-titanium oxide), fergusonite (rare earth-iron-titanium oxide), hausmannite (manganese oxide), gemat (iron oxide), ilmenite (iron-titanium oxide), perovskite (calcium titanium oxide), periclase (manganese oxide), polycrase (rare earth-yttrium-titanium-Nabieva-tantalum oxide), pseudobrookite (iron-titanium of the led),the members of the pyrochlore group such as, for example, betafit (rare earth-calcium-sodium-uranium-titanium-Nabieva-tantalum oxide-hydroxide), microlith (calcium-sodium-tetralogy oxide-hydroxide fluoride), pyrochlore (sodium-calcium-niobium oxide-hydroxide fluoride) and the like, or any combination containing at least one member of the pyrochlore group; ramsdellite (manganese oxide), romanechite (hydrated barium-manganese oxide), group members of rutile, such as, for example, cassiterite (tin oxide), platelet (lead oxide, pyrolusite (manganese oxide), rutile (titanium oxide), stishovite (silicon oxide) and the like, or any combination containing at least one of the above members of the group rutile; area(Y) (rare earth-yttrium-iron-titanium oxide), senarmontite (antimony oxide), members of the spinel group, such as chromite (iron chromium oxide), franklinite (zinc-manganese-iron oxide), ganit (zinc-aluminum oxide), magnesiochromite (magnesium-chromium oxide), magnetite (iron oxide) and spinel (magnesium aluminum oxide) and the like, or any combination containing at least one of the above members of the spinel group; tapeit (beryllium-magnesium-aluminum oxide), tantalite (iron-manganese-santalova-niobium oxide), Tapiola (iron-manganese-santalova-niobium oxide), uraninite (the oxide is wound), Valentina (antimony oxide), zinc (zinc-manganese oxide, hydroxides such as, for example, brucet (magnesium hydroxide), gibbsite (aluminum hydroxide), goethite (oxide-hydroxide of iron), limonite (hydrated oxide-hydroxide of iron), manganite (oxide-hydroxide of manganese), psilomelan (barium-manganese oxide-hydroxide), romaic (calcium-sodium-iron-manganese-antimony-titanium oxide-hydroxide), seefeldt (silver-antimony oxide hydroxide), stibiconite (oxide hydroxide antimony), etc. or any combination containing at least one of the above materials.

Suitable examples of materials which modify and use in the substrate are layered clay (e.g., expanded vermiculite), flaked graphite, blown glass or silica, hollow glass spheres, foamed glass spheres, cenospheres, ceramic, foamed slag, sintered bauxite, sintered silica, etc. or any combination containing at least one of the above materials. Typical inorganic substrate can be based on sand, crushed glass beads, sintered bauxite, sintered alumina, mineral fibers, such as zircon and mullite and the like, or a combination containing one or more inorganic substrates. Hollow glass spheres can be purchased from companies is Diversified Proppants.

Suitable examples of organic materials are used as substrate are ground or crushed shells of nuts, ground or crushed fruit pits, processed wood, milled or crushed animal bones or any combination containing at least one of natural fillers. For example, suitable organic materials are natural organic fillers, which contain milled or crushed walnuts, ground or crushed pecans, ground or crushed almonds, ground or crushed grain palm tree, ground or crushed Brazil nuts, or a combination containing one or more of the above nuts. Other examples of suitable organic materials are ground or crushed grain plums, ground or crushed grain peach, ground or crushed grain cherry, ground or crushed shells of olives, ground or crushed shells of apricots, ground or crushed husk maize kernels, processed wood materials from oak, Hickory, walnut, poplar and mahogany, which were processed by grinding or chipping.

In another typical embodiment, neo the organic substrate has a bulk density from about 0.6 to about 1.0 g/cm 3and apparent density of from about 1.3 to about 2.0 g/cm3. Inorganic substrates are characterized by the percentage of the test crushing, less than or equal to about 20%, when subjected to the test for crushing API RP 60 at about 16.9 MPa (2000 psi). Inorganic substrate has a circularity from about 0.6 to about 0.9, and the sphericity of from about 0.6 to about 0.9.

The density of the substrate can be selected depending on the application, which is intended for the proppant. It is advisable to choose the substrate that can give the proppant apparent density of from 1 to 4 g/cm3. Apparent density is defined as the density of the proppant (i.e. the weight per unit volume of the material, including the inherent proppant void). In one of the embodiments, the substrate has an apparent density from about 1.4 to about 1.9 g/cm3. In another embodiment, the substrate has an apparent density from about 1.5 to about 1.85 g/cm3. In yet another embodiment, the substrate has an apparent density of from about 1.6 to about 1.80 g/cm3. Optimal apparent density of the substrate is equal to about 1.80 g/cm3. The substrate covered with the help of this method, such as sand, have an apparent density of about 2.65 g/cm3and different forms of ceramics have tightly the TB of 2.5-3.4 g/cm 3.

C. Composite particle-substrate

As follows from the above example in figure 3, the substrate 21 may include a deformable composite particle containing a homogeneous particle, which contains the fine particles 22 of the filler, held together utverzhdennym or at least partially utverzhdennym binder 24. Various embodiments of these composite particles are additionally described below and in U.S. patent No. 6406789, U.S. patent No. 6632527, U.S. patent No. 6582919 and in the publication of the patent application U.S. No. 2006/0078682 (McDaniel et al.), all of which are fully incorporated into the present application as reference material.

In this case, the individual particles, which are combined with the formation of the substrate can have an average particle size of 2 to 30 μm. In one of the embodiments of the particles, which aglomerados with the formation of the substrate 21 may have average particle sizes less than or equal to 28 μm or less than or equal to 25 μm, or less than or equal to 20 μm, or less than or equal to 15 μm. Can be used bimodal distribution of particle sizes or distribution of higher-order modality.

Filler 21 may be particles or fibrous fillers. Fibrous fillers typically have an aspect ratio greater than 1. In accordance with the concepts of the present application "hair is NISTO" fillers may exist in the form of whiskers, needles, rods, tubes, strands, elongated platelets, lamellar platelets, ellipsoids, microfibers, nanofibers and nanotubes, elongated fullerenes, etc. If these fillers are in aggregate form, unit aspect ratios greater than 1, would also be consistent with the purposes of the present invention. Examples of such are well known in the art fillers are fillers that are described in "Plastic Additives Handbook, 5thEdition" Hans Zweifel, Ed, Carl Hanser Verlag Publishers, Munich, 2001. He limiting the invention, examples of suitable fibrous fillers include short inorganic fibers, including processed mineral fibers such as those obtained from mixtures containing at least one of the following components: aluminium silicates, aluminium oxides, magnesium oxides, and calcium sulfate hemihydrate, boron fibers, ceramic fibers such as silicon carbide and fibers from mixed oxides of aluminum, boron and silicon, sold by 3M Co., St. Paul, MN (USA) under the trade name NEXTEL®. To the fibrous fillers are also single crystal fibers or "whiskers", including silicon carbide, alumina, boron carbide, iron, Nickel, copper. Can also be included, and such fibrous fillers as glass fiber, basalt fibers, including textile glass is Alekna, and quartz.

Also included organic and natural fibers, such as wood flour obtained by spraying the wood, and fibrous products such as cellulose, cotton, sisal (bast fiber), jute, canvas, cotton fabric, hemp fabric, felt, starch and natural cellulose materials, such as Kraft paper, cotton paper and paper containing fibre, starch, cork flour, lignin, ground nut shells, husks of corn and rice and the like, or any combination comprising at least one of the above materials.

In addition, in the composite substrate can be used synthetic reinforcing fibers. These include organic materials capable of forming fibers such as phenolic fiber, polyethylene terephthalate, polybutylene terephthalate and other polyesters, polyarylate, polyethylene, polyvinyl alcohol, polytetrafluoroethylene, acrylic resins, highly resistant fibers with high heat resistance, comprising an aromatic polyamide, polyaramide fibre", such as a commercially available fiber from Du Pont de Nemours under the trade name KEVLAR, polybenzimidazole, polyimide fibers, such as fibers, which can be obtained from Dow Chemical Co. under the trade names POLYIMIDE 2080® and PBZ® fiber, polyster, polyester-ether-keto is, the polyimide, polybenzoxazole, aromatic polyimide or polyester-imides, etc. Can be also used a combination of any of the above fibers. The best fibers fibers are phenolic resins.

In one of the typical embodiments of the fiber phenolic resin and fiberglass can be used as the fibrous filler in the composite substrate. Useful glass fiber can be made of any type capable of forming fiber glass compositions and include fiberglass, made from capable of fiberizing glass compositions, commonly known as "glass", "glass", "glass", "glass D", "glass R","glass's", as well as derivatives of E-glass, not containing fluorine and/or not containing boron. Glass AR can be used due to its resistance to alkalis. In the composite substrate can be industrially produced glass, usually with nominal diameters of the fibers from about 4.0 to about 35,0 μm, and the most widely produced fibers of E-glass, having nominal diameters of the fibers from about 9.0 to about 30,0 µm. It is also possible and the use of fibers with non-circular cross sections. Fiberglass can be glued or nakleenyi. Laminated glass can be coated on at the ore part of its surface sizing composition, selected for compatibility to present on the substrate surface. A sizing composition facilitates the removal of moisture and full hydration of the coating on the strands of fibers to achieve the desired physical properties in the composite.

Fiberglass are predominantly sized glass strands. In the manufacture of optical fibers multiple threads can be molded simultaneously, glued celanova coating agent and then grouped into what is called a strand. Alternatively, you may first be molded itself strand of yarn and then glued. The amount of sizing is usually the quantity that is sufficient for binding glass fibers into a continuous strand and which is from about 0.1 to about 5 wt.% and more typically from about 0.1 to about 2 wt.% based on the weight of the fibers. Generally, it can be about 1.0 wt.% based on the weight of fiberglass. Can also be used fiberglass in the form of chopped strands of a length of approximately one quarter inch or less and preferably a length of one-eighth of an inch. If desired, they can be longer than about a quarter inch in length.

The fibers used in the composite substrate may have a length of from about 6 to about 3200 μm. In one of the embodiments of the length in the curl amount from about 10 to about 1600 μm. In another embodiment, the length of the fibers is from about 10 to about 800 μm. Optimal fiber is shorter than the greatest diameter of the composite substrate.

The diameter of the fibers (or, in the case of fibers with non-circular cross-section, the hypothetical size equal to the diameter of a hypothetical circle which has an area equal to the cross-sectional area of the fiber) is from about 1 to about 20 μm. The aspect ratio (ratio of length to diameter) may be in the range of from about 1 to 20 μm. The aspect ratio (ratio of length to diameter) may be in the range of from about 5 to about 175. The fiber may have a round, oval, square, rectangular or other acceptable cross-section. The fibers may be straight, twisted, curled or combine several of these forms.

One of the most common fillers used in the organic coating is silica flour. Quartz powder typically has a particle size less than or equal to about 20 μm. In one embodiment, the implementation of the quartz powder has a particle size less than or equal to about 10 μm. In another embodiment, quartz powder has a particle size less than or equal to about 5 μm. An example of a commercially available silica flour is SIKRON® SF 242, which offers Quarwerke GmbH, Frechen, Germany.

C. Hybrid particle-substrate

As follows from figure 5, another type of substrate is a hybrid particle-substrate 42 having the inorganic particle 44 as core and utverjdenie or at least partially utverjdenie floor (composite layer) 46, which contains inorganic fillers or organic fillers 48. Organic coating 46 may optionally be applied either as a single layer or as multiple layers.

Fillers 48 in the composite layer 46 hybrid particle-substrate 42 can be the same as described above for the composite particles of the substrate.

Various embodiments of these hybrid particles are additionally described in the provisional application for U.S. patent No. 60/611350 registered on 20 September 2004, and the publication of the patent application U.S. No. 2006/0078682 Al (McDaniel et al.), which are fully incorporated into the present application as reference material.

In a typical embodiment 4, when the substrate is coated particle contains a single particle, typical synthetically prepared inorganic substrate contains one or more of the following compounds: silicon oxide (SiO2), aluminum oxide (Al2O3), titanium dioxide (TiO2), iron oxide (II) (Fe2O3), calcium oxide (Cao), magnesium oxide (MgO), aluminum oxide to the lia (K 2O) and sodium oxide (Na2O). The inorganic substrate can also contain a sulfite ions, water and carbon dioxide in trace quantities less than or equal to about 2 wt.% based on the weight of the substrate.

Synthetically prepared organic substrate may contain thermoplastic polymers, thermosetting polymers, or a combination containing any thermoplastic polymer or thermosetting polymer. Examples of suitable organic materials which can be used as a substrate, serve as precursors to polymers (i.e. low molecular weight substances such as monomers, dimers, trimers and the like), polymers, copolymers such as block copolymers, star block copolymers, ternary copolymers, statistical copolymers, alternating copolymers, graft copolymers and the like; dendrimers, ionomers and the like, or any combination containing at least one of the above polymers. If the substrate contains any thermosetting polymer, it is desirable that the organic materials were subjected to curing (cross-linking) when exposed to thermal energy, electromagnetic radiation, or a combination comprising at least one of these effects. To induce curing can be initiated. Can be used is also and other additives, enhancing or regulating the curing, such as accelerators, inhibitors, etc.

Examples of suitable thermosetting polymers for use in dry (directionspanel) top layer 46 of the substrate are epoxy resin, acrylate resin, methacrylate resin, phenol resin, epoxy-modified novolak, furan resins, urea-aldehyde resins, melamine-aldehyde resins, polyesters, alkyd resins, phenol formaldehyde novolak, phenol formaldehyde resole, phenol-aldehyde resins, rezol and Novolac resins, epoxy-modified phenolic resins, Polyacetals, polysiloxane, polyurethane, etc. or any combination containing at least one of the above-mentioned thermosetting polymers.

D. Resin and powders curing the outer layer

The outer organic coating contains curing the audio record in the form of a continuous phase and any reactive and/or directionspanel powder. Under the outer organic coating refers to the top of the resin coated particles in a continuous phase and any powder embedded in this phase or protruding from it. Resale include phenol formaldehyde resole, phenolformaldehyde and furfuryl alcohol or furfuryl aldehyde resole, or phenolformaldehyde the rezol resin, substituted with alkyl phenols or oil from the seeds of the cashew nut. Allowed resale for solvent and water-based. Resale additionally described below. Rezol resin coating of the present invention are low viscosity liquid resins that can be applied to the substrate at low temperatures from about 10°to about 66°C, mainly from about 21°to about 49°C, as indicated in the description, and have an induction period of curing, allowing the resins to show their performance in their application in the underground reservoir. However, these resins are not goodnaturedly resins that can react at a temperature of 65°C or below without the use of additional heat. The induction period associated with the use of these rezol coating resins is a characteristic that distinguishes these rezol resin from goodnaturedly resins, such as, for example, goodnaturedly resin type modified alkali resolv described in published patent application U.S. No. 2006/0078682 A1 (McDaniel et al.), paragraph 0043. Modified alkali the audio record is produced by adding potassium hydroxide or sodium hydroxide to rezol the resin so that a sufficient portion of the resin becomes melodramaticheskiy salt of the resin, which can be overiden obrabatyvaimym esters without increasing the temperature. Used in the present invention resale external coatings do not contain named melodramaticheskij salts. Rezol resin outer coating of the present invention are latent, but cured by heating, so that they can be cured at elevated (above 70°C and typically above 80°C) temperatures existing in the underground reservoir.

Reactive powders contain one or more of the following polymers: novolak (with or without hexamethylenetetramine), resale, polyesters with a hydroxyl functions (reactive towards razolam), polyacrylates with a hydroxyl functions (reactive towards razolam) and functionalityand polyurethanes, which must be reactive towards razolam, such as polyurethane, having an amine or hydroxyl functions. Typically, the average particle size of the reactive powder is about 200 mesh (74 μm) or less.

Directionspanel powders may be any inorganic or organic powders, which are not chemically active with respect to solid rezol the floor. Examples of inorganic directionspublic powders include quartz flour, crushed glass and minerals. Examples of organic directionspublic powders include ina crushed shells of nuts, and other natural organic materials, such as wood flour obtained by spraying the wood, and fibrous products such as cellulose, cotton, sisal (bast fiber), jute, canvas, cotton fabric, hemp fabric, felt and natural cellulose materials, such as Kraft paper, cotton paper and paper with glass fiber, starch, cork flour, lignin, ground nut shells, husks of corn and rice and the like, or any combination comprising at least one of the above-mentioned materials. Typically, the average particle size directionspanel powder is about 200 mesh (74 μm) or less.

1. Rezol resin

In one of the embodiments of the present invention uses a coating that includes phenol-aldehyde rezol polymer in the form of a solution or dispersion. Rezol resin can also be used as a powder for embedding or bonding to contain the audio record to the floor. As a rule, rezol powder has an average particle size of about 200 mesh or less and recovered by using a spray drying method to preserve the reactivity of the audio record.

Used to cover rezol resin is liquid when applied to a substrate and, thus, has a molecular weight suitable for the liquid state. Typical Molek is popular weight the average for liquid audio record is from about 400 to about 2000. The resin coating is cured. Rezol resin coatings are offered in the form of a wet aqueous solution and dried by the method of the invention, while still in the uncured (unstitched).

Used for powder rezol resin is solid when it is applied to the coated substrate and, thus, has a molecular weight, suitable for solid state. Typical molecular weight, average for solid audio record is from about 500 to about 5000. The resin coating is cured. Rezol powder can be applied in the uncured state. Preferably, rezol powder was reactive in relation to himself, and liquid audio record was sticky (wet during application).

Preferred rezol resins are rezol resins with a low content of free phenol: below 3 wt.% and preferably below 2 wt.% the free phenol.

In the phenol-aldehyde rezol resin molar ratio phenol/aldehyde is from about 1:1 to about 1:3, typically from about 1:1 to about 1:1,95. One of the preferred ways of receiving rezol resin is a combination of phenol with any source of aldehyde, such as formaldehyde, acetaldehyde, propionic aldehyde, FSD is oral, benzaldehyde or paraformaldehyde, under alkaline catalysis. During this reaction, the aldehyde is present in molar excess. Preferably, rezol resin had a molar ratio of phenol to formaldehyde is from about 1:1.1 to 1:1,6. A typical way to obtain resolu is to put the phenol in the reactor, to add alkali catalyst (sodium hydroxide or calcium hydroxide) and the aldehyde, for example 50%by weight solution of formaldehyde, and to carry out the reaction of the ingredients at elevated temperature until the desired viscosity and the disappearance of free formaldehyde. The water content was adjusted using distillation. To increase the elasticity or plasticity of the binder may also be present sastifactory or plasticizers. Can contain other known additives.

Resolume can be traditional resale or modified resole. Modified resole disclosed in U.S. patent No. 5218038 fully incorporated into the present application as reference material. Such modified resole obtained by reaction of the aldehyde with a mixture of unsubstituted phenol and at least one phenolic material selected from the group which includes arilena, alkyl phenol, alkoxyethanol and aryloxides. Modified rezol resins include alkoxy-modified rezol resin. From al the hydroxy-modified rezol resins preferred methoxy-modified rezol resin. However, phenolic rezol resin, which is preferred, is a rezol resin containing o-benzyl ether obtained by reaction of any of the phenol with an aldehyde in the presence of aliphatic hydroxycodone containing in the molecule two or more hydroxyl groups. In one preferred modification of the method the reaction is carried out in the presence of any monohydroxy alcohol.

The phenols and the aldehydes suitable for the production of modified containing o-benzyl ether of phenol rezol resins are, as a rule, any of phenols and aldehydes which can be used for the formation of phenolic resins. Suitable for the production of modified phenolic resins metalline catalysts include salts of divalent ions of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca, and VA. Tetraalkoxysilane the compounds of formula Ti(OR)4where R denotes an alkyl group containing from 3 to 8 carbon atoms, are also catalysts suitable for this reaction. The preferred catalyst is zinc acetate.

To obtain modified rezol resins use a molar excess of aldehyde to 1 mol of phenol. Preferably, the molar ratio of phenol to aldehyde was in the range of from about 1:1.1 to about 1:2,2. The reaction of the phenol with the aldehyde is traveling in the presence of the ion of the divalent metal as a catalyst at a pH below about 7. To the reaction mixture aliphatic gidroksosoedinenii, which contains in the molecule two or more hydroxyl groups. Gidroksosoedinenii added at a molar ratio of hydroxycodone to phenol is from about 0,001:1 to about 0.03 to:1.

Suitable hydroxidealuminum, which contain in the molecule two or more hydroxyl groups are compounds having a hydroxyl number from about 200 to about 1850. The hydroxyl number is determined by the standard method with acetic anhydride and expressed in mg KOH/g hydroxycodone. Suitable hydroxycodone include ethylene glycol, propylene glycol, 1,3-propandiol, diethylene glycol, triethylene glycol, glycerol, sorbitol and polyester-polyols having a hydroxyl number above about 200.

After adding to the reaction mixture hydroxycodone containing in the molecule two or more hydroxyl groups, continue heating until then, until you react from about 80 to about 98% of the aldehyde. Modified phenolic audio record can be "completed" so that goes to form the alkoxy-modified phenolic rezol resin. In the process of completing one of the hydroxyl groups into alkoxygroup using traditional methods that would be obvious to specialists familiar with the present disclosure.

Resolu also include ternary copolymer of phenol, furfuryl alcohol or furfuryl aldehyde and formaldehyde.

Ternary copolymer of phenol/formaldehyde/furfuryl alcohol produced by the catalytic reaction of phenol, formaldehyde and furfuryl alcohol, where the catalyst is a water-soluble salt of polyvalent metal, which (reaction) is carried out in a substantially aqueous environment. Conventional water-soluble salts of polyvalent metals, which can be used as a catalyst in the present invention, less expensive compared to soluble in organic solvents equal equivalents of metal ion used in the method described in US 4255554 (Wuskell). The use of water-soluble salts of polyvalent metal eliminates the need for pH control of the reaction as it is necessary to do in case of an acid catalyst. However catalyzed salt of polyvalent metal reaction should be carried out at a pH lower than 7.0. If uncontaminated phenol, formaldehyde, furfuryl alcohol and zinc acetate or lead to mix in due proportion, the pH will always be lower than 7.0.

The water-soluble salts of polyvalent metals used as catalysts for the above ternary copolymer include polyvalent ions of manganese, zinc, cadmium, magnesium, cobalt, Nickel, tin, copper, iron, lead and calcium. Site is titlename catalysts are zinc acetate, lead acetate and mixtures thereof.

Response to receipt of said ternary copolymer can be conducted by introducing first, in the reaction of furfuryl alcohol and formaldehyde at a temperature of from about 85 to 105°C at atmospheric pressure, then adding the phenol and continuing the reaction until a viscosity of approximately 100 to 10000 CPS, mainly from about 200 to 5000 SP, measured at a temperature of about 25°C. However, this reaction can be conducted at elevated temperatures up to about 140°C. in a sealed reaction vessels, ensuring that the reaction mixture boiled under these more stringent conditions. The reaction can also be carried out by introducing first, in the reaction of phenol and formaldehyde, then adding furfuryl alcohol, and continuing the reaction until a viscosity of approximately 100 to 10000 CPS, mainly from about 200 to 5000 SP, measured at about 25°C. alternatively the reaction can be conducted by introducing the reaction of a phenol, furfuryl alcohol and formaldehyde simultaneously in the presence as catalyst of water-soluble salts of polyvalent metals. The obtained ternary copolymer of phenol/formaldehyde/furfuryl alcohol can be used either as such or diluted in any suitable solvent, including furfuryl alcohol and water.

Typically, the molar ratio of phenol to furfuryl alcohol can vary from the use of the but of 0.1:1 to about 10:1. The molar ratio of formaldehyde to phenol+furfuryl alcohol can vary from about 0.5:1 to 2:1, respectively, in moles CH2O:(phenol+furfuryl alcohol). The amount of catalyst can vary from about 0.2 to about 8 wt.% from the total amount of phenol and furfuryl alcohol.

Although the above reaction refers to formaldehyde may also be used and other aldehydes of General formula R-CHO, where R is a hydrocarbon radical containing about 1-8 carbon atoms, such as acetaldehyde, Propionaldehyde, furfural, paraformaldehyde, a solid low molecular weight polymer of formaldehyde, etc. Preferred form of formaldehyde is water-type form of formalin.

Can be used furfuryl alcohol or substituted furfuryl alcohol derivatives of the formula I

in which R3can refer to alkyl, aryl, alkenyl, alkalol, alkoxy, aryloxy, halogen, hydrogen or hydroxyacyl. The preferred compound is furfuryl alcohol.

Along with this, although phenol is the preferred phenolic reactants may be used and other substituted phenols, in particular phenols of the formula II

in which R4, R5and R6can independently denote hydrogen, is levoberegnyi radicals, occupiedthe radicals, hydroxyradicals or halogen and arranged so that either the two ortho-positions, or one ortho and one para-position, or two ortho and two para-positions are unsubstituted. As a rule, suitable for use phenols are phenols which are suitable for the production of phenolic resins. Some examples are o-cresol, m-cresol, p-cresol, op, Nonylphenol, 3,5-dimethoxyphenol, p-tert-butylphenol, p-butoxyphenol, resorcinol, 3,5-Xylenol, 3,5-dieselfuel, catechin, 3,5-dibutyltin etc.

After their application as coatings called ternary copolymers can be solidified using hardeners, such as an acid catalyst, such as ammonium chloride or ammonium sulfate. Ternary copolymers disclosed in provisional patent application U.S. No. 60/385578, registered 5 June 2002, included in the present application as reference material.

If desired rezol floor or rezol powder may contain a curing agent such as hexamethylenetetramine.

2. Novolac polymer-containing resin

In one of the embodiments of the present invention use a powder that includes phenolaldehyde Novolac polymer.

The novolak may be any novolak used with proppants. Novolak can be obtained by reaction of a doubt is a phenolic compound with an aldehyde in a strong acidic region of pH. Appropriate acid catalysts include strong mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid and organic acid catalysts such as oxalic acid and p-toluensulfonate acid. One of the alternative ways of obtaining nofollow is the reaction of any of the phenol with the aldehyde in the presence of divalent inorganic salts, such as zinc acetate, zinc borate, salts of manganese, cobalt salts, etc. the Choice of catalyst can be important for the direction of the production novolaks, which have different relationships ortho - and para-substitution of the aldehyde to the phenol ring, for example zinc acetate favours ortho-substitution. Novolak enriched ortho-substituents, in other words, high-ortho-Novolac may be preferred due to the greater reactivity in the subsequent cross-linking in the evolution of the polymer. High-ortho-Novolac discusses KOR and Pilato in Phenolic Resins, pp.50-51 (1985) (Springer-Verlag), included in the present application as reference material. High-ortho-Novolac defined as novolak, in which at least 60% of the total ortho - and para-substitution is ortho-substitution and predominantly ortho-substitution is from this amount, at least about 70%.

N is kolacny polymer contains, generally, the phenol and the aldehyde in a molar ratio from about 1:0.85 to about 1:0.4. For this purpose, can be used with any suitable aldehyde. The aldehyde may be formaldehyde, paraformaldehyde, formaldehyde, acetaldehyde, furfural, benzaldehyde or other aldehyde sources. Preferred the formaldehyde.

Novolac resins are mainly Novolac resin with a low level of free phenol, which they contain less than 1 wt.% and more preferably less than 0.6 wt.%.

The molecular weight of the novolak should vary from about 500 to 10,000, mostly from 1000 to 5000, depending on the intended their use. Molecular weight of novolaks or other polymers in this description of the present invention, unless otherwise indicated, represents srednevekovoi molecular weight. Particularly preferred high-ortho Novolac resin.

Composition Novolac resins contain, as a rule, at least 10 wt.% Novolac polymer, predominantly at least about 20 wt.% Novolac polymer and most preferably from about 50 to about 70 wt.% Novolac polymer. The remainder of the resin composition may include cross-linking agents, modifiers and other suitable ingredients. Phenolic fragment Novolac polymer is selected the C phenols of the formula III or bisphenol formula IV, respectively

and

where R and R1independently represent alkyl, aryl, arylalkyl or N. In formula III, R and R1are located mainly in the m-position to the hydroxyl group in the corresponding aromatic ring. Unless otherwise stated, the alkyl is defined as having from 1 to 6 carbon atoms, and aryl is defined as having a ring of 6 carbon atoms. X in formula IV represents a direct link, sulfonyl, unsubstituted or halogen-substituted alkylidene, cycloalkyl or halogensubstituted cycloalkylation. Alkyliden is a divalent organic radical of the formula V:

When X is alkylidene, R1and R3chosen independently from H, alkyl, aryl, arylalkyl, of halogensubstituted alkyl, halogen-substituted aryl, and halogen-substituted of arylalkyl. When X is halogen-substituted by alkylidene, one or more hydrogen atoms alkylidene fragment of formula V is substituted by a halogen atom. Halogen mainly is fluorine or chlorine. Similarly, halogensubstituted cycloalkylation substituted in cycloalkylation fragment predominantly fluorine or chlorine.

Typical phenol of formula III is the phenol. Typical bisphenol formula V include bisphenol a, bisphenol s, s, bisfe the ol E, bisphenol F, bisphenol S and bisphenol Z.

Novolac polymers can contain any of the phenols of the formula III, bisphenol formula IV, or a combination of one or more phenols of the formula III and/or one or more bisphenols formula IV.

Phenolic Novolac for practical purposes, do not harden when heated and remain soluble and fusible, unless there is any hardener (cross-linking agent). Thus, during the curing of Novolac resin cross-linking agent is used to overcome the deficit of groups associated alkionovymi bridges, with the aim of transforming the resin into an insoluble and infusible state. Appropriate cross-linking agents include hexamethylenetetramine (NEH), paraformaldehyde, oxazolidine, melamine resin or other donors aldehydes and/or described above rezol polymers. Each of these cross-linking agents can be used by itself or in combination with other crosslinking agents. Rezol polymer may contain substituted or unsubstituted phenol.

Powder composition Novolac resins of the present invention contains, as a rule, up to about 25 wt.% The NEH and/or to about 90 wt.% rezol polymer based on the total weight of the coating composition. When the NEH is the only cross-linking agent, it contains about is about 5 to about 25 wt.% the resin. When only cross-linking agent is phenolaldehyde the audio record, the resin contains from about 20 to about 90 wt.% rezol polymer. The composition can also contain combinations of these cross-linking agents.

To obtain a phenolic Novolac polymers with one or more phenols of formula III phenol is mixed with an acid catalyst and heat. Then to the hot phenol with add catalyst at elevated temperature aldehyde, for example 50%by weight solution of formaldehyde. The resulting reaction water is removed by distillation, resulting in a gain of molten novolak. Molten novolak then cooled, rasclaat and grind into powder.

To obtain a Novolac polymers with bisphenolate formula IV bisphenol mixed at an elevated temperature with any solvent, for example n-butyl acetate. After that add an acid catalyst such as oxalic acid or methansulfonate acid, then BPA, mix, and finally add the aldehyde, usually formaldehyde. After reacting substances refluxed. It should be noted that the preparation of the Novolac resin may be performed under conditions of acid catalysis or catalysis with divalent metal (such as Zn, Mn), where BPA is present in more hemakumara the number in relation to the source of the aldehyde. After boiling the water collected by azeotropic distillation with n-butyl acetate. After removal of water and n-butyl acetate resin rasclaat, receiving resin products. Alternatively, the polymers can be obtained by using as the solvent is water.

Novolac polymer may be in some cases additionally modified by the addition of VINSOL®, epoxy resins, bisphenol a or other known resin additives. One method of obtaining modified with alkyl phenol phenol Novolac polymer is a combination of alkylphenol and phenol in a molar ratio higher than 0.05:1. Such a combination is introduced into reaction with a source of formaldehyde under conditions of acid catalysis or catalysis of divalent metals (such as Zn, Mn). During this reaction, the combination of an alkylphenol and phenol is present in a molar excess relative to the formaldehyde present.

If desired phenolaldehyde Novolac or bisphenol-aldehyde novolak can be modified by the reaction of these novolaks with additional aldehyde using a basic catalyst. Typical used catalysts are sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide or lime), ammonium hydroxide and amines. If phenolaldehyde polymers or bisphenol-alder is the breaking of the polymer molar ratio of added aldehyde to phenolic fragment (calculated on the monomer units of the phenolic fragments in the novolak) is from 0.4:1 to 3:1, mainly from 0.8:1 to 2:1. The result can be cross-linked (reactive) polymer having different chemical structures and, as a rule, a higher molecular weight compared to rezol polymers obtained with the one-stage method, which includes the initial mixing bisphenol monomers and aldehyde with an alkaline catalyst at the same reaction molar ratio of combined aldehyde and bisphenol. In addition, really should use various aldehydes at different stages of obtaining the polymer. These polymers can be used by themselves or together with other polymers, such as phenolaldehyde Novolac, bisphenol-aldehyde novolak, or a combination of, as a crosslinking agent or as a component of cross-linking agents. If-modified aldehyde polymers are used as cross-linking agents can be used together with other typical cross-linking agents such as those described above with reference to Novolac polymers.

3. Polyester resin

In one of the embodiments of the present invention use a powder that includes reactive complex polyester.

Used in this application, the term "polyester" refers to the "homopolymers", and "copolyesters and implies a synthetic polymer, obtained by polycondensation of bifunctional carboxylic acids with at least one bifunctional hydroxyl compound, for example valovym, or glycol component. Typical polyesters are those which contain unsaturated (vinyl) end groups and which otverzhdajutsja in the presence of peroxide catalysts. To make these polyesters any desired properties can be mixed with other monomers. To speed up the curing polymerization catalysts of the type of benzoyl peroxide may also be used together with catalysts based on metals, such as cobalt salts.

In particular, the polyesters for powder contain hydroxy-functional polyacrylates having reactivity against resolu. These polymers suitable for the present invention include polyhydroxylated polyesters. Polyhydroxylated polyester polymers (with functionality equal to 2 or greater) are formed by the reaction of polycarboxylic acids or anhydrides (typical examples: isophthalic acid, phthalic acid or its anhydride, maleic acid or its anhydride, fumaric acid, sabotinova acid, azelaic acid, adipic acid, trimellitate acid or its anhydride, etc. with polyhydroxylated compounds, such as ethylene glycol,propylene glycol, neopentylglycol, butyleneglycol, 1,4-butanediol, hexyleneglycol, 1,6-hexanediol; polyglycols, such as diethylene glycol or triethylene glycol, etc.; triola, such as glycerin, trimethylacetyl, trimethylolpropane etc. and other more vysokodetalnye alcohols, such as pentaerythritol, sorbitol, lures, etc. Polyhydroxylated polyesters additionally described in U.S. patent No. 4920199 included in the present application as reference material.

4. Acrylic polymers

Acrylate polymers for use in reactive powders of the present invention are polymers, commonly called acrylic substances, polyacrylates or acrylate polymers. Some of acrylate monomers (component polymers)used for the formation of acrylate polymers, can be acrylic acid, butyl acrylate, 2-etelgisille, methyl acrylate, acrylate, Acrylonitrile, n-butanol, methyl methacrylate, 2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate and TMRCA (trimethylolpropane-triacetate). The acrylate-ion (CH2=SSOO-) is ion of acrylic acid. The acrylate is a salt or ester of acrylic acid. They are also known as propenoate (since acrylic acid is also known as 2-Papanova acid). Acrylates contain vinyl groups, i.e. linked by a double bond atoms ug is erode, directly attached to the carbonyl carbon. The acrylates and methacrylates (salts and esters of methacrylic acid) are common monomers for acrylic polymers. Dried by spraying the latex is also suitable acrylic polymer. In particular, acrylates for powders contain hydroxy-functionalityand the polyacrylates or amino-functionalityand the polyacrylates, showing reactivity against razolam.

5. Urethane resin

Polyurethane resin is obtained by mixing the polyisocyanate component, polyhydroxylated component or polienovogo component with the catalyst. As a rule, polyhydroxyethyl component is polyhydroxy component dissolved in any solvent. Polienovy component may be polyfunctional and is chosen such as to obtain still retains reactivity oligomerization polyurethane. Solvent, as a rule, mixtures of hydrocarbon and polar organic solvents, such as organic esters. Typical hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, a mixture of high-boiling aromatic hydrocarbons, heavy naphtha, etc.

a. Polyhydroxy component

The floor of the hydroxyl component, as a rule, is a phenolic rezol resin or alkoxy-modified rezol resin, as described above.

b. Isocyanates

Isocyanate component may be varied within wide limits and has a functionality equal to 2 or higher. In accordance with the determination of this application polyisocyanates include isocyanates having a functionality equal to 2 or higher, for example, diisocyanates, triisocyanate etc. Typical suitable isocyanates are organic polyisocyanates, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and their mixtures, in particular their crude mixture, which are available on the market. Other typical polyisocyanates include methylene-bis(4-phenylisocyanate), n-paxildiscount, naphthalene-1,5-diisocyanate, cyclopentane-1,3-diisocyanate, p-delete the entry, toluene-2,4,6-triisocyanate and triphenylmethane-4,4',4”-triisocyanate. Higher isocyanates receive liquid reaction products: (1) diisocyanates and (2) polyols or polyamines and the like can also be used isothiocyanates and mixtures of isocyanates. Also provided many of the crude or crude MDI, which are available on the market. Particularly preferred for use in the invention are polyacrylonitrile having the following General formula (VI):

in which R is chosen from g is uppy, consisting of hydrogen, chlorine, bromine and alkyl groups having from 1 to 5 carbon atoms; X is chosen from the group consisting of hydrogen, alkyl groups having from 1 to 10 carbon atoms, and phenyl; and n has an average value is typically from about 0 to about 3. The preferred polyisocyanate may vary depending on the particular system in which the used powder.

Urethanes are disclosed in U.S. patent No. 5733952 (Geoffrey).

E. Additives

Additives used in special cases for special needs. The resin systems of the invention can include a large variety of additional materials.

In order to enhance coating adhesion to the substrate resin may include one or more additives, such as are usually added to the liquid resin agent combinations, such as silane.

Such agents combinations include, for example, organosilane, which are known agents of the combination. Examples of suitable agents of the combinations of this type include aminosilane, epoxysilane, mercaptoethane, hidroxizina and freedomline. Particularly preferred application organofunctional silanes as agents in combinations to improve mipomersen organic-inorganic adhesion. Such organofunctional silanes are described by the following formula (VII):

,

in which R denotes a reactive organic group, OR a14means vysokomobilnuju alkoxygroup, such as co3or OS2H5. Especially valuable for a combination of phenolic or furan resins with silicon oxide are amidofunctional silanes, which can serve as Union Carbide A-1100 (gamma-aminopropyltriethoxysilane). The silane may be pre-mixed with the resin or added separately to the mixer.

The organic coating may in some cases contain additives such as silicone lubricants, surfactants, wetting agents, dyes, pigments, flow modifiers (such as regulating the flow of agents and flow amplifiers), hardeners, cross-linking agents, initiators, stabilizers, anticorrosion additives, antioxidants, fire tools, agents that prevent scapania, antiozonants, stabilizers, anticorrosion additives, anti musty agents, fillers, antistatic agents, waxes and the like, or a combination containing at least one of the above additives.

Surfactants may be anionic, nonionic, cationic, amphoteric or mixtures thereof. Some surfactants also act as regulating the flow of agents. Other additives include protivopolozhnostei and heat-resistant additives. Of course, additives may be added in combination or singly.

If desired, the organic coating may in some cases contain as dust additive thermoplastic elastomer to reduce dust compared to the same particle, but not containing thermoplastic elastomer. Some dust additives include ethylene-butyl acrylate copolymers (Exxon-Mobil). There are other examples, such as novolak and resole, modified Acrylonitrile-butadiene rubber (NBR), which can act as modifiers toughness.

If desired, the organic coating may in some cases contain the modifier toughness. Modifier toughness can give organic coating elastic properties. Suitable modifiers for toughness include natural and synthetic elastomeric polymers, usually on the basis of such monomers as olefins (e.g. ethylene, propylene, 1-butene and 4-methyl-1-penten), alkanolamine monomers (such as styrene and α-methylsterol), conjugate diene (for example, butadiene, isoprene and chloroprene and vinyl carboxylic acids and their derivatives (for example, vinyl acetate, acrylic acid, alkylacrylate acid, acrylate, methyl methacrylate and Acrylonitrile). They include th polimery and statistics, block, radial block, grafted copolymers, copolymers of type "core-shell" or any combination containing at least one of the above-mentioned polymers.

A particularly valuable class of modifiers toughness includes copolymers of the type AB (double) and AVA (triple), and grafted copolymers of the type "core-shell" alkanolamides and diene compounds, especially those that contain styrene and either butadiene or isoprene units. The conjugated diene blocks may be partially or fully hydrogencarbon, after which they can be presented in the form of ethylene-propylene blocks, etc. and have properties similar to olefin block copolymers. Examples of suitable three-block copolymers of this type are polystyrene/polybutadiene/polystyrene (SBS), hydrogenated polystyrene/polybutadiene/polystyrene (SEBS), polystyrene/polyisoprene/polystyrene (SIS), poly(α-methylsterol)/polybutadiene/poly(α-methylsterol) and poly(α-methylsterol)/polyisoprene/poly(α-methylsterol). Particularly preferred three-block copolymers are commercially available HYCAR from a Noveon or KRATON D®and KRATON G®from the Shell.

Suitable as modifiers toughness are also grafted copolymers of the type "core-shell"that can be fully or frequent is a rule neutralized with metal ions. Usually grafted copolymers of the type "core-shell" are the core mainly of a conjugated diene or crosslinked acrylate rubber and one or more shells, the cured core and obtained on the basis of monoalkanolamines and/or acrylic monomers, alone or in combination with other vinyl monomers. Other modifiers for toughness include the above types containing units having polar or active functional groups, and a variety of polymers, such as Cycoloy rubber (Thiokol), polysulfide rubber, polyether rubber (for example, polypropyleneoxide), epichlorhydrin rubber, ethylene-propylene rubber, thermoplastic polyester elastomers, thermoplastic ether-esterne elastomers and the like, and mixtures containing any of the above-mentioned polymers. Suitable impact modifier viscosity of the ionomer resin is SURLYN®from the company Du Pont.

When the organic coating is used many layers, toughness modifiers can be used in any of these layers. Generally, it is desirable to use modifiers for toughness in the layer located on the substrate. Modifiers for toughness can be used in amounts greater or equal to approximately 0.5, predominantly greater or equal to about 1.0 andmore preferably greater or equal to about 1.5 wt.% calculated on the total weight of the organic coating. Generally, it is desirable to have the toughness modifier that is present in a quantity less than or equal to about 20, mostly less than or equal to about 15 and more preferably less than or equal to about 10 wt.% calculated on the total weight of the organic coating.

F. the Manufacture of coated particles

For the preparation of coated particles or particles for gravel packing mix the appropriate substrate (e.g., single particle, the composite particle or a hybrid particle), wet resin and the dry resin powder under conditions that provide curable coating compositions. In the variants of implementation, in which the substrate using the composite particles or hybrid particles, organic material, used in curing the outer layer may be the same or different from that used in the composite substrate or a hybrid substrate, provided that the coating resin material suitable for curing and resin composite substrate or a hybrid substrate at least partially overiden.

The substrate with the desired thermosetting polymer or a precursor of thermoset polymer is placed first in the mixing device and mixed with formation of a given first mixture at a temperature of from about 10 to p is IMEMO 66°C, mainly from about 21 to about 49°C. Thermosetting rezol polymers or precursors of thermosetting rezol polymers are liquids at room temperature. Before mixing with thermosetting polymer or a precursor of thermoset polymer substrate is usually not pre-heated. When mixing the liquid thermosetting rezol polymer or thermoset precursor rezol polymer is located on the substrate, forming an organic coating. Before or during mixing of the substrate with a liquid resin, it is desirable to add to the mixture the agent combinations. Suitable agents of the combination is indicated in the present description.

Mixing can be carried out in the device, which employs the power shear, longitudinal force, pressure, ultrasonic energy, electromagnetic energy, thermal energy, or any combination containing at least one of these forces and energies, and is conducted in processing equipment in which these forces are implemented using a single screw, multiple screws, interchangeable rotating in one direction or protivovazdushna screws, not interchangeable rotating in one direction or protivovazdushna screws, reciprocating screws, screws with pins, drums with pins, skrypko, rollers,plungers, helical rotors, or combinations containing at least one of these factors. Typical mixing devices are extruders, such as single-screw or twin-screw extruders, Buss mixer kneader, mixer Helicon, the mixer of Ariha, WARING blenders, mixers hensely, mixer periodic operation of Barber Green, ribbon blenders, etc.

After that directionspanel and/or reactive powder add to first mixture of coated particles and mixed for a sufficient time before the formation of the second mixture of engineering covered by the audio record of the particles having directionspanel powder and/or reactive predominantly Novolac or rezol powder embedded in or adhering to the floor. The amount of liquid coating resin and the amount of powder is selected depending on the desired amount of the coating, as a rule, the ratio of liquid resin and powder may vary depending on temperature and time of adding different ingredients. A typical value may be adjusted, to avoid the limits of technology, in particular sticky particles from one limit and pulverized particles have a different limit. Performance characteristics of the product may depend on the level of the applied resin in combination with liquid resin and powder, as well as from selected see the crystals and powder.

If desired, can be applied using one or more coatings of a liquid resin and powder. Additional coatings can be applied by coating on a particle having a single coating of resin and powder, an additional coating of liquid resin and subsequent deposition of additional portions of the powder to the additional liquid coating, then this operation if desired, repeat. Preferably the application of a sufficient amount of resin to achieve a loss on ignition (based on the combined weight of the coating) from about 0.3 to about 5 wt.%, mainly from about 0.3 to about 4 wt.%, with one or more outer layers of curable rezol coating with reactive powder.

Typically, the silane is added to the sand in the mixer and after about 10-20 seconds, for example after 15 seconds, add liquid audio record. The silane could be mixed with audio record previously. For example, at 1000 g sandy substrate is used from 7.0 to 10.4 g of liquid audio record (containing 65% solid material). After about 30-50 seconds after adding audio record type of the reactive powder.

The powder is preferably added after 60 sec after the first silane and, respectively, by 45 seconds after adding liquid audio record. However, these moments add depends on the speed of mixing, as well as from the temperature of the environment and the design of the mixer. In the best example of coated particles obtained in laboratory conditions (23°C, mixer Hobart), the silane is added to the substrate and allowed to stir for 15 seconds, then add liquid rezol resin, continuing the stirring for another 45 seconds, and then add the powder, which takes an additional 240 seconds (300 seconds for the entire cycle) to complete the formation of dry engineering particles.

It is desirable to add to the mixture lubricating means at any time before the product will "disintegrate" on lukosiute particles. Lubricating means when the temperature of mixing should preferably be liquid and have a high enough boiling point to avoid its losses during mixing. Suitable lubricants include Dow Corning 200 Silicone, mineral oil, paraffin wax, vaseline, cocamidopropyl-hydrocolloid (Chembetatine CAS from Chemron Corp., Paso Robles, California) and synthetic lubricating means ACRAWAX ST - bis-stearamide any diamine (from Glyco Chemicals, Inc., Greenwich, Connecticut). The amount of lubricant may be from about 0.01 or 0.03 to about 0.5 wt.% in calculating the weight of a granular material.

After or simultaneously with the adulteration to the coated substrates of the reactive powder can be added in small quantities directionspanel organic or neorg the technical powdered fillers. In the case of their application directionspanel powdered fillers are taken at less than about 10% of the number of reactive powders. The size of the particles directionspublic organic or inorganic powdery fillers are typically from about 2 to about 30 μm.

Then get particles with a curable coatings.

In one of the typical methods of producing coated particles in the mixer type mixer Ariha load the mixture containing the substrate, thermosetting polymer or a precursor of thermoset polymer, which should be used for organic coatings, Novolac powder or rezol powder and possible additives. Mixing must be carried out within a certain time at a first speed. Next, the stirring speed change. The change of the stirring speed contributes to the formation of a layer of organic coating around the substrate, resulting in a gain of particles of the desired size, i.e. from about 200 to about 800 μm. To obtain the desired density of coated particles can change the parameters of the process. For example, to change the density of the coated particles, it is possible to increase the amount of filler or the amount of organic material.

G. particle Parameters

For okharakterizovanie h is STIC of the present invention can be used with the following parameters.

1. The amount of resin

The amount of resin can be determined by measuring the weight loss on ignition (LOI). LOI is usually defined in a two-hour test in the furnace, which is preceded by pre-conditioning of several crucibles with lids in the oven, heated up to 927°C. the Crucible with a lid put then in the oven at 927°C, which give then re-heated to 927°C and withstand the crucible at 927°C for 15 minutes so Prepared crucibles and lids are placed in the desiccator, which are standard dehumidifiers, and leave to cool to room temperature. Air-conditioned crucible with lid then weighed and placed in a crucible 8 g of coated resin sand. Next, the crucible with the lid and the sample is re-weighed and then closed the lid of the crucible with the sample placed in an oven at 927°C, which give then re-heated to 927°C, and incubated the sample in the furnace after repeated temperature in the furnace 927°C for 2 hours. Then the crucible with the lid and the sample is transferred into a desiccator and allowed to cool to room temperature. Weighed again using analytical scales cooled crucible with lid and sand sample and calculate the loss of weight on ignition of each sample as the difference between initial and final weight of the sample.

2. A particle size of

Coated particle and heat, typically, the average size of from about 200 to about 2000 μm (from about 70 to about 10 mesh). In one embodiment, the implementation of the coated particle has a size from about 300 to about 1000 μm (from about 50 mesh to about 18 mesh). In another embodiment, coated particle has a size of from about 350 to about 650 μm (about 45 mesh to about 28 mesh). Coated particles may have a bimodal distribution or distribution higher modality. Typically, reactive and/or directionspanel powder has an average particle size of about 200 mesh (about 70 mesh) or less.

3. Density

It is desirable that the coated particles had a bulk density of from about 0.75 to about 0.95 g/cm3. In one embodiment, the implementation of the coated particles have a bulk density from about 0.8 to about 0.9 g/cm3. In one embodiment, the implementation of the coated particles have a bulk density from about 1.7 to about 3.6 g/cm3. Coated particle has an apparent density from about 1 to about 4 g/cm3by definition method API RP 58 with isobutyl alcohol. In one embodiment, the implementation of the coated particle has an apparent density of from about 1.1 to about 3 g/cm3. In another embodiment, coated particle has an apparent density is t about 1.15 to about 2 g/cm 3. It is desirable that the coated particles had an apparent density of from about 1.6 to about 3.6 g/cm3. The density can be varied either by changing the density of cores/substrates, or changing the choice of filler, or producing both.

4. Not limited tensile strength at compression

The limit of compressive strength curable proppants is defined as the limit of compressive strength, measured according to the following procedure, known as the test is not limited to the limit of compressive strength (UCS). In this test, the proppant is added 2%by weight KCl solution (with the addition of a small amount of detergent to enhance wettability). The KCl solution and the proppant (approximately 6 to 18 and, as a rule, 12 pounds (5,46 kg) of proppant per gallon (3.78 l) KCl) gently mix to wet proppant. Remove possible trapped air bubbles. To remove these bubbles if necessary, use a wetting agent. This suspension (approximately 100-200 grams depending on density) is transferred into a parallel cylinders of stainless steel with an outer diameter of 1.25 inches and a length of 10 inches, equipped with valves at the top and bottom to pit if necessary, the pressure of liquid or gas, pressure gauge, counting up from 0 to 2000 pounds/inch (0-16,9 MPa) and a floating piston to transmit pressure to the sample. Generally load Faure is on at least 3, preferably at least 6 samples so as to provide a length in excess of double the diameter of the end of the rod. During application of the voltage, the lower valve is open, allowing fluid to drain from the slurry, after which when exposed to a temperature close. The test cylinder is connected to a nitrogen cylinder and he is under the influence of pressure 6950 MPa propagated to the sample moving pistons, and then the upper valve is closed, while the lower valve remains open. As soon as the temperature approaches the valve for a fluid medium to form the bottom valve (valve for the fluid) is closed. Too early closing of the valve for the fluid can cause pressure sufficient (as a heating element) to prevent/reduce the desired closing pressure acting on the rod proppant. Too late closing of the valve can cause loss of too much fluid from the rod as a result of evaporation or boiling.

Contains a sample of parallel cylinders is transferred to a furnace pre-heated to the set value, i.e 200±1°F (about 93±0.5°C), and remain in the furnace for 24 hours while maintaining during the curing pressure and temperature. The pressure should be maintained within ±10%. In the curing process, which is s-curable proppant particles into a consolidated mass. At the end of 24 hours, the cylinders extract, quickly relieving the pressure and removing the fluid, and then consolidated core sample size of 1 inch x 6 inch vyrisovyvaet from the cylinder. The sample is allowed to cool and air dry for about 24 hours and cut (usually sawn) on the compression rods with respect to the diameter/length (D/L) to about 1:2.5 or more. The air drying is carried out at a temperature below about 49°C. Typically, both ends of each terminal line, getting a flat parallel surface, after which the rods are cut, maintaining the ratio of diameter/length (D/L) to about 1:2.5 or more.

The compression rods installed in a hydraulic press and exert force between parallel planes at a rate of approximately 1820 kg/min until breakage of the rod. For rods with compressive strength less 4,28 MPa use the speed of load application 455 kg/min Record the force required for failure, record the results of repeated measurements and calculate the limit of compressive strength for each sample using the following formula. To determine this value for the sample coated with resin proppant use the average value of repeated measurements.

(Fc, lb/inch)=4×Fg/{(p×d2)[0.88+(0.24d/h)]}

where Fc=the ultimate strength in compression (lbs/inch);

Fg hydraulic pressure gauge (pound force);

p=π (3,14);

d=diameter (inches);

h=length of rod (inches).

The ultimate compressive strength of the cores is determined with the aid of a hydraulic press, in particular Carver Hydraulic Press, model #3912, Wabash, Indiana. Typical limits the compressive strength proppants of the present invention are in the range from 0.45 to 25 MPa or higher. However, the reproducibility of the test for a limited ultimate compressive strength (UCS) is at best ±10%. Usually the individual resin layers of the invention have limits UCS above 4,3 MPa, as described in detail below. It was also noted that the test for limit of compressive strength can be used to specify whether the floor utverzhdennym or cured. No clutch or consolidation of coated particles after wet compression at 8,45 MPa and 93°C for a period of time up to 24 hours indicates the cured material.

5. Roundness

It is desirable that covered the particle had a circularity from about 0.7 to about 0.9. The typical roundness equal to about 0.8. It is also desirable that covered the particle had the sphericity of from about 0.7 to about 0.9, measured according to API RP 58 (Procedure 58 recommended by the American petroleum industry).

6. The acidity of the aqueous extracts

The following description relates to a test procedure, which measures "sweet is the activity of water extracts coated resin sand". This test is not a measure of the acid solubility of the coated resin proppant. It refers to the measurement of the impact of extractable water (cover) substances can have on the pH of the water (or pH of the system fluid for hydraulic fracturing).

Test the acidity (relating to covered with the resin proppants) is a measure of the level of acidity of the aqueous extracts with resin proppants. This test has to do with the effect, which is covered with resin proppant (and extractable water in the coating components) should have on the pH of the system fluid for hydraulic fracturing, which should be used for transporting proppant in formed as a result of fracturing the crack.

The acidity is determined as follows. Prepare a large number (about 1000 ml) quietly boiling distilled or deionized water, using the first heating plate and chemical glass and regulating the heat so that the boiling was weak and sustainable. The temperature should be approximately 100°C depending on the altitude. On the second heating plate increase the setting value of the temperature selector. 250-millimeter graduated glass is placed a portion of 50 g of resin. Put a glass covered with resin proppant in the second heat athelney plate. Quickly add boiling deionized (distilled) water to the level of 125 ml glass coated with resin proppant and shake the glass to remove bubbles. Leave the mixture before boiling, which requires about 15-30 seconds, and allow the mixture to boil for 3 minutes Place the beaker in the ice bath and stirred until the water temperature has 21-27°C. the Proppant coated with curable and partially utverzhdenii resin hardens, giving a solid mass. This mass during cooling, the suspension must be broken down with a spatula. Initially stirred with a spatula to break up the mass of the coated resin proppant, and then stirred with a thermometer. To minimize the need for full cooling time, stirred long enough, and the water level in the ice bath remains at least as high as the level of liquid in the glass.

After cooling the suspension to room temperature again add in a glass of deionized water to the mark of 125 ml, which is to fill the water that could be lost during boiling, and immediately measure the pH of the aqueous layer using a standardized pH meter. Record the initial pH with an accuracy of up to 0.05 units. When the pH electrode is not in the layer of proppant. Using 0.1 G. of sodium hydroxide octarepeat suspension to pH=9,00. Registrera the t volume of titrant, required for reaching the end point pH with an accuracy of up to 0.05 ml and register the endpoint pH with an accuracy of up to 0.05 units.

7. Test on extraction with acetone

Test on extraction with acetone is another method of determining whether a coating or coating uncured. In the method by extraction with acetone is dissolving the resin fraction, which is not overiden. This test is conducted by placing pre-weighed dried sample (approximately 50 g) is covered with the resin particles with known content of the resin coating device socket and boiling condensation of acetone over the material within 2 hours. After drying the thus treated sample change the content of the resin is expressed as the percent extractable with acetone resin. More specifically, since the uncured resin soluble in acetone, and the cured resin in acetone insoluble, boiling condensate of acetone will remove only the uncured fraction. By weighing the sample before and after boiling acetone and determination of the percent change calculated the degree of cure. For example, weight loss in the case of a typical covered utverzhdenii resin sand may have only 5% of the LOI of the sample. Thus, for the sample with 2.0 g LOI, destruction 2.0 g as a result of extraction with acetone should mean that the way the C is cured 100%.

8. The test temperature adhesion

The test temperature adhesion is another indicator of whether the coating is cured. The test is carried out by placing the covered material on the heated bar to determine the melting temperature and determining the lowest temperature at which the material is coated sticks."Temperature adhesion above 175°C at most the hot end of the strap usually indicates the cured material depending on the resin system. Strap to determine the melting temperature is a brass bar (18 inches long and 2 inches wide) with elektroobogrevatelnye element at one end. Thus, the length of the strap can be mounted temperature gradient and the temperature along the placket traced with the help of thermometers or thermocouples.

Using a funnel on the hot bar impose a uniform band of about 100 g is covered with a resin substrate, such as sand, and utverjdayut within 60 seconds. After that the bar cant, to allow the uncured proppant to fall off. Melting point is the lowest temperature at which the coated resin sand forms a solid mass and does not fall off away from the bar, when it tilted ninety degrees. As a rule, utverjdenie floor has a temperature adhesion in which the limits of from 65 to 150°C, for example, from 93 to 120°C.

9. The wettability of the particles in the water

Wettability to determine the number of selected surface-active substance or substances (surfactants), need(s) for wetting proppant(s), determine to establish the amount of surfactant needed to reduce aeration/trapping air to zero.

Prepare a dilute surfactant solution and fill them with 25-ml glass burette.

Usually the degree of dilution is 1:100. However, many surfactants may be tested undiluted. Later in 300-ml beakers (which has dwindled form) from Brasilia pour 200 ml of 2%KCl solution (you can also use deionized water). Put a glass under the beater, adjustable autotransformer (VARIAC), or a mixer with a built-in speed regulator so that the blade was at a distance of approximately 1/4” (6.5 mm) from the bottom. The glass shall be secured in place by means of the ring support and clamp. Then place in a suitable position the burette, put the switch the mixer OFF (disabled) and translate the speed control to the highest position at which the contents of the glass (sand in water) will not be discarded. Then start the mixer and add the test amount of proppant.

In table a illustrates the typical limits retrieve and proppant.

Table a
Limits download proppant
lb/Gal (g/l)g/200 ml
248
496
6144
8192
10240
12288 (preferred)

Further stirred for 5 seconds and stop stirring, visually checking the presence of air bubbles adhering to the surface of grains of proppant. If the bubbles are not visible, the proppant consider completely soaked. If air bubbles exist, add 1/4 ml of surfactant, re-run the mixer for 10 sec and again checks for the presence of air bubbles adhering to the surface of the proppant. If the newly visible bubbles, repeat the operation to add a surfactant, mixing and visual inspection up until a large part of the bubbles disappear, then reduce surfactant additive to 1/8 ml When bubbles are no longer visible, record the amount of surfactant required for when Oceania proppant.

Repeat the test as follows to be more close to practical conditions in the field.

Prepare another sample of water and add to the water the exact number of diluted surfactant (as defined in the first procedure at the time when the proppant was completely soaked). Then set the Cup under the mixer and run the mixer. Add the specified amount of proppant. Mix 10 sec and stop the stirrer. Check and record the relative amount of air bubbles on the surface of the proppant. If there is some amount of bubbles, the titration is continued as before until the bubbles disappear and will not require additional surfactant. Register additional amount required surfactant.

Calculate the amount of surfactant required for complete hydration of the proppant.

VV(SAS), Gal/1000 Gal=1000×((VSAC×Frasb)/Vmix)

when X pound prop/Gal.

VM(SAS), Gal/1000 Gal=119.831×((VSAC×Frasb)/Mprop

each pound prop/Gal,

where VV- the amount of surfactant to wet the proppant, Gal/1000 Gal under x lbs prop/Gal;

VM- the amount of surfactant to wet the proppant, Gal/1000 Gal/lb, prop/Gal;

Frasbthe dilution ratio, the amount of surfactant/volume of diluent, dimensionless;

p> Vsurfexperimental volume of diluted surfactant, ml;

Mpropis the mass of the test proppant, g;

Vmix- the volume of the mixture of proppant/water, Jr.

10. Test the turbidity of

Particles is tested for turbidity as follows. A portion of 15.0 g of deionized/distilled water with the addition of 0.1% of the fluorinated surfactant FSO placed in a clean cuvette for samples (Hach catalog #21228 or equivalent) and install in place of the threaded cap of the cell. FSO obtained from duPont Fluorosurfactant ZONYL™ FSO. Wipe the cuvette outside resorcinol paper. Make sure no bubbles on the surface of the cell bubbles. Place the cuvette in the turbidimeter (HACH Model 2100 P) and read turbidity units NTU values (units of turbidity). Weigh 5,00 g measured sample and place it in the cuvette. Using a vortex mixer (Thermolyne Maxi-Mix 1 or equivalent) the mixture of the sample/water, stirred for 10 minutes Again cleanse the outside of the cell resorcinol paper. Again cuvette placed in the turbidimeter and read the turbidity after 30 sec after mixing using a vortex mixer. Register turbidity units NTU for this sample as "dust".

Particles of the present invention mainly reach the measured turbidity below 100 NTU after processing in a ball mill for 30 minutes, less than 200 NTU after processing in chalk ball is nice for 60 min and/or below 300 NTU after processing in a ball mill for 150 minutes Coated particles are, as a rule, the turbidity of less than or equal to about 250 when measured according to API RP 56.

N. The use of particles as proppant

Described in the present invention the particles are cured coating. Therefore, they can be pumped into the underground reservoir and to cure the coating in an underground reservoir. They can be pumped into an underground stratum as the only proppant 100%proppant packing (formed when the hydraulic rupture fracture) or as a partial replacement of the existing commercially available ceramic and/or sand origin proppants coated with resin and/or uncoated, or as mixtures with them, for example so that the coated particles ranged from 10 to 50 wt.% from being pumped into the well of proppant. For example, after first pre-cured proppant or uncoated proppant pumped into the well, the curable proppant (the present invention) can be placed in the crack, which is closest to the wellbore, or in holes cracks. This type of operation hydraulic fracturing is carried out without stopping the replacement of proppant and has in the industry known as "operation of fastening the wall."

In the case of curable proppants method may include curing curable resin composition at who is actvie on the composition sufficient heat and pressure in the underground reservoir, to ensure cross-linking of the resin curing and consolidation of the proppant of the present invention. In some cases, to facilitate consolidation curable proppant can be used as an activator. In another embodiment, using the curable resin composition on the proppant, the method further includes low-temperature kislotosoderjasimi curing at temperatures up to the lower limit of 21°C. the Sample low-temperature kislotnoschelerngo curing disclosed in U.S. patent No. 4785884 fully incorporated into the present application as reference material.

Curable coated particles of the invention are particularly promising as in the case of use as a proppant as such, and in case of their use in conjunction with other proppants as the tail of the material after use of uncoated proppant or pre-cured coated proppant, or any other curable proppant, being the fraction closest to the wellbore.

I. the Use of coated particles as gravel packing and to prevent the ingress of sand into the well

It is known that an oil or gas well provide a gravel packing around their trunks. Another aspect of the present izobreteniyami is these gravel packing can be achieved with coated particles of the present invention.

These coated particles, it is advisable to apply in standard sizes, characteristic of the gravel used in gravel packing. As a rule, the strength requirements for particles of proppant used in the completed gasket cracks are more stringent than in the case of gravel packing. Gasket gravel may serve to prevent the inflow into the well of sand to prevent the flow of formation fines from the formation into the wellbore.

Operations gaskets gravel-covered particles can be suspended in the carrier fluid and pumped into the well, which should be placed gravel packing. The carrier fluid flows into the subterranean zone and/or returns to the surface, while the coated particles remain in the underground area. The resulting gravel gasket acts as a filter to separate the reservoir sand from the produced fluids, while allowing the produced oil and/or gas to flow into the wellbore. The method of forming a gravel packing includes, therefore, the suspension of coated particles in the carrier fluid with the formation of the slurry, pumping the suspension into the well and the drainage of the carrier fluid with the formation of gravel packing. B is duci laid on the place, entered particles otverzhdajutsja with the formation of a permeable solid barrier that retards the progress of the sand.

Another example is the use of coated particles to fill any cylindrical structure containing the granular resin material, i.e. proppant, with subsequent introduction into the well. Being laid on the place, covered with particles act as a filter or screen to eliminate reverse flow of sand and other proppants or particles of the underground reservoir. Eliminating reverse flow of granular material in ground-based equipment is a significant advantage. This is achieved by pre-filled gasket screens, which are covered with resin sand or ceramics are subjected to curing before the screen Assembly is placed in the well.

The following examples, which are typical and are not limiting of the scope of the invention, illustrate compositions and methods of production of some of the embodiments described in the application of coated particles.

EXAMPLES

The following examples serve to illustrate the present invention. Unless otherwise indicated, all parts and percentages are given by weight and all measurements in screening sacks meet the standards of the US Standard Screen sizes. Given in the examples of the silane pre which is an adhesion promoter a from Union Carbide Corporation. The proppant was coated liquid EHE and sales phenol rezol resin manufactured by Hexion Specialty Chemicals, Inc., Louisville, Kentucky. Used for proppant powder layer is SD909A: powdered phenol-formaldehyde novolak with 15% of hexamethylenetetramine, representing sales phenol-formaldehyde novolak produced by Hexion Specialty Chemicals, Inc., Louisville, Kentucky. Powder SD909A has a range of particle sizes, providing a passage through a sieve of 200 mesh.

EXAMPLE 1

This experience was carried out to determine the properties of the coated particles of the present invention. The cycle of the coating was carried out as follows. 1000 g of ceramic particles CARBOPROP® 12/18 intermediate density at room temperature is loaded into a laboratory Hobart mixer. Start the stirrer. Then add 0.8 g 1100 (aminopropyltriethoxysilane) and include a timer (0:00 min). After 30 seconds add 10.0 g EHE (phenol-formaldehyde liquid audio record). When the timer shows 2 min, added with continuous stirring to 18.4 g of powdered phenol-formaldehyde novolak SD909A with 15% of hexamethylenetetramine (approximately 2.4% of the total amount of organic material on the particles). When the timer shows 12 min, weight is engineering and retrieve it from the mixer. After that, the product experience in those is giving 24 hours using UCS test on the strength of binding under conditions to 8.45 MPa at 93°C, that gives 4,99 MPa.

EXAMPLE 2

This experience was carried out to determine the properties of the coated particles of the present invention. The cycle of the coating was carried out as follows. 1000 g of ceramic particles CARBOPROP® 12/18 intermediate density load at room temperature in a laboratory Hobart mixer. Start the stirrer. Then add 0.8 g a (aminopropyltriethoxysilane) and include a timer (0 min). After 30 seconds add 10.0 g EHE (phenol-formaldehyde liquid audio record). When the timer shows 2 min, added with continuous stirring 33,2 g powder SD672D (phenol novolak without hexamethylenetetramine) (approximately 2.4% of the total amount of organic material on the particles). Powder SD672D has a particle size of about 100 mesh. When the timer shows 12 min, weight is engineering and retrieve it from the mixer. After that, the product experience within 24 hours using the UCS test on the strength of binding under conditions to 8.45 MPa at 93°C, which gives the remaining 9.08 MPa.

EXAMPLE 3

Curable resin coating is produced by adding 0.4 g of agent combinations (silane A-1100) to 1 kg of the substrate with constant stirring. After 15 sec after the silane is added to the cycle liquid audio record (OWR-262E supplied by the company Hexion Specialty Chemicals, Inc., Louisville, Kentucky). Powdered Novolac resin FD900-A (with 7% of hexamethylenetetramine use isout for sample preparation, D and G) or powdered Novolac resin SD-909A (15% of hexamethylenetetramine is used for preparation of samples a, b, E and F), each of which is obtained from Hexion Specialty Chemicals, Inc., Louisville, Kentucky, add in the loop when reading timer 2 minutes the Material is stirred for another 4 minutes and unloaded from the mixing device. When using the above procedures analytical properties changed when evaluating different options resins, tar, particle sizes and substrates. The concentration of hexamethylenetetramine was varied from 7 to 15%, depending on what powder is used in a particular composition (see data analysis in tables 1, 2 and 3).

5 is a photograph of a sample prepared in the laboratory of the particles (as such) for the case of the sample And when the magnification of about 10X.

6 is a photograph of a sample prepared in the laboratory of the particles (as such) for the case of the sample at magnification of about 10X.

7 is a photograph of a sample prepared in the laboratory of particles for the case of the sample at magnification of about 10X after the test for an unlimited ultimate strength in compression when 8,45 MPa.

Fig is a photograph of a sample prepared in the laboratory of particles for the case of the sample at magnification of about 10X after the test on the ultimate tensile strength.

At a certain material was evaluated sintering PU is eating space 50 g of coated material in a cylindrical container with a 1 kg load on it and place the container for 24 hours in an oven, heated at temperatures 37-60°C (see data analysis in tables 1, 2 and 3).

Table 1
The measured property
Sample numberAndInD
Sand, API cell size API, par value40/7040/7040/7040/70
The addition of silane A-1100, weight (g)/time (sec)0,4/00,4/00,4/00,4/0
Add audio record OWR 262E, weight (g)/time (sec)10,4/157,0/158,6/155,2/15
Adding powder SD A, weight (g)/time (sec)23,0/6020,0/60
Adding powder FD-900A, weight (g)/time (sec) 21,5/6011,5/60
The download time in seconds300300300300
The resin content, LOI, wt.%2,982,142,461.19
Melting point (sticking), °F[°C]204 [96]214 [101]<185 [85]<185 [85]
The tensile strength of hot tensile, MPa0,10,037
The particle size distributions
Sieve No.(US Standard) [mm]
30 [0,589]0,10,10,00,0
40 [0,42]6,07,76,07,5
45 [0,351]10,210,522,224,2
50 [0,297]38,034,948,848,7
60 [0,249]25,524,514,613,9
70 [0,211]17,919,67,65,6
80 [0,150]2,32,60,80.1
pan [<0,150]0,00,10,00,0
Total100,0100,0100,0100,0
in the amount of(-40+70) [-0,42+0,211]to 91.6 to 89.593,292,4

Table 2
Sample numberAndInD
The turbidity values of the units of turbidity233125
Unlimited tensile-compression
Voltage close at 93°C, 24 h in 2% KCl,12 lb/Gal added at 0.0 MPa405 [2795]210 [1449]305 [2105]85 [587]
Voltage close at 93°C, 24 h in 2% KCl, 12 lb/Gal added at 6.9 MPa1325 [9143]508 [3505]955 [6590]231 [1594]
Voltage Zack is itia at 66°C, 24 hours in 2%10341
KCl, 12 lb/Gal added at 0.0 MPa
Voltage closing at 66°C, 24 h in 2% KCl, 12 lb/Gal added at 6.9 MPa14681
The tendency to agglomeration@41,6°Ceasy flowabilityeasy flowability
@51,6°Ceasy flowabilityeasy flowability
@ 59,9°Ceasy flowabilityeasy flowability
Clusters, wt.%1,0 1,01,01,0
The efficiency of coating, wt.%100,0100,0100,0100,0
the pH of an aqueous extractThe initial pH8,98,8
ml of 0.1 N. NaOH to pH=90,40,3
ml of 0.1 N. NaOH to pH=104,64,4

/tr>
Table 3
SampleEFG
12/18CarboProp500 g1000 g1000 g
A-11000.4 g 0.4 g0.4 g
OWR-262E5.0 g10.6 g10.6 g
SD-909A8,2 g32,4 g-
FD-900A--32,4 g
---
The melting temperature (adhesion), °C<85<85<85
wt.% LOI2,143,803,75
The limit of compressive strength, MPa (1K) @ 93°C4,1416,9014,79
The limit of compressive strength, MPa @ 93°Cto 9.93the 7.43
The tensile strength of hot tensile, MPa1,891,961,02
The initial pH8,628,72
ml to pH=90,90,7
ml to pH=107,65,6
pH (aqueous suspension)7,798,13
Cycle times add
Time=0: add agent combinations
Time=30 sec: add audio record
Time=2 min: adding PF-powder
Time=12 min: unloading
SST (initial temperature of the sand)=ambient temperature

The above data show that the application of sand or ceramic substrates of the liquid phenol-audio record at room temperature followed by the introduction of powdered phenol-formaldehyde Novolac resin (with or without the improved properties of hexamethylenetetramine) with the result to obtain high-performance engineering-coated resin particles, which can be used as oil proppant.

EXAMPLE 4

This example shows that the delay in adding the powder (after silane and audio record) leads to drying of the audio record and is the reason that the audio record loses the ability to hold powder. Adding Novolac powder with a delay in time shows the influence of free (not adhering) of the powder to the substrate, due to partial drying of liquid audio record by passing cycle. After coating on four separate download with different time adding each material is screened through a sieve of 100 and 200 mesh. Assembled on the pallet nepitavshie powder is weighed. Table 4 shows the times add powder and specified nepitavshie residual powder phenol-formaldehyde resin, appearing after the preparation of each sample. Other times in the cycle times add such as those listed in table 4.

7.0 g of liquid audio record (OWR-262E)obtained from Hexion Specialty Chemicals, Inc., Louisville, Kentucky, add in cycle 15 sec after the silane. At the same time added to 20.0 g of powdered Novolac resin (FD900-A, obtained from Hexion Specialty Chemicals, Inc., Louisville, Kentucky) variout first experience of the powder added after 1 min in the time cycle. In subsequent experiments, the powder added later, as shown in the table . The results below show that the delay adding powder quantity naritaweg powder increases.

Table 4
Add powderNepitavshie residual PF-powder
1 min1.04 g
2 min2,01 g
3 min2,96 g
4 min2,98 g
Ingredients:
1000 g wet sand
7.0 g of liquid audio record OWR-262E
20,0 g powdered Novolac resin FD900-A

EXAMPLE 5

Conducted an additional test to establish the influence of the treatment process, namely adding the powder to the sandy substrate before adding liquid audio record. Phenol-formaldehyde powder is added by a 15 sec after adding liquid audio record at the 60th second in the same cycle time of 300 sec. The material is divided into three phases: the units of the audio record, plus sand, neprestaly powder and in a small degree the Yeni coated substrate.

Figure 9 (12X zoom) shows the aggregates (clusters) of the audio record and sand obtained by sieving the sample to a small extent covered substrate. Figure 9 shows the number of units that contain a large amount of resin. This sample was tested on the mass loss on ignition (LOI) and found that his LOI is to 19.1 wt.%. This indicates that the liquid resin is not effective for coating particles of a uniform layer. Instead of coating the particles of the substrate, rezol resin is mostly concentrated with the formation of aggregates with several grains and powdered resin.

Figure 10 (with magnification 30X) shows another sample to a small extent covered substrate, which was used "as such" and not sifted. Figure 10 shows a large number of not adhering to the substrate powder. This sample was tested on LOI and discovered that his LOI 1.99 wt.%. The presence of large quantities of naritaweg powder indicates the impossibility of achieving a homogeneous mixture of powder and substrate before adding the liquid resin. Add liquid resin will only lead to the formation of aggregates, as in Fig.9, creating a situation in which the surface of the substrate is not sticky with respect to the remaining powder.

While the invention is described on the basis of typical embodiments for the special the sheets is obvious, what can be made of various kinds of changes and features of the invention may be replaced by equivalents without departing from the scope of the invention. In addition, many modifications can be made in order to adapt a particular situation or material to the idea of the invention without straying beyond its essence. In other words, it is assumed that the invention is not limited to a specific embodiment, disclosed as the best method is provided for implementing the present invention.

1. Engineering particles coated with a size of from about 6 to about 200 mesh, and each particle includes: a substrate selected from the group consisting of:
particle-substrate containing an inorganic material and, optionally, at least partially utverjdenie floor,
particle-substrate containing an organic material and, optionally, at least partially utverjdenie floor,
composite particles containing essentially homogeneous molded part containing the first portion of binder, and filler particles dispersed throughout the mentioned first portion of a binder where the specified first portion at least partially overiden, and where the size of the filler particles ranges from about 0.5 to about 60 microns (μm); and
hybrid particles containing a composition layer, located on the inorganic core particle, and a composite layer contains at least partially utverjdenie organic coating and filler particles, and the size of the filler particles ranges from about 0.5 to about 60 μm; and
coating located on the substrate, and the coating contains a continuous phase containing curable rezol phenol-formaldehyde resin, and a reactive powder particles embedded in a continuous phase or glued to it, and the powder particles contain at least one component selected from the group consisting of rezol phenol-formaldehyde resin, phenol-formaldehyde Novolac resin of ester, acrylic compounds and urethane.

2. Particles according to claim 1, in which the substrate has a size in the range from 6 to 100 mesh.

3. Particles according to claim 1, in which the substrate has a size ranging from 12 to 80 mesh.

4. Particles according to claim 1, characterized by mass loss on ignition of from about 0.3 to about 5 wt.%, attributed to the coating on the substrate.

5. Particles according to claim 4, in which the substrate is a particle-substrate containing an inorganic material.

6. Particles according to claim 1, in which the substrate is a particle-substrate containing an organic material.

8. Particles according to claim 7, in which the substrate is a composite particle, coated particle is characterized by loss of weight on ignition of from about 7 to about 20 wt.%.

9. Particles according to claim 1, in which the substrate is a hybrid particle.

10. Particles according to claim 1, in which the reactive powder particles have an average particle size of about 200 mesh or less.

11. Particles according to claim 1 in which the curable rezol phenol-formaldehyde resin continuous phase contains free formaldehyde in the amount of less than about 3 wt.%.

12. Particles according to claim 1, in which the reactive powder particles contain powder rezol phenol-formaldehyde resin with a content of free formaldehyde is less than about 3 wt.%.

13. Particles according to claim 1, in which the reactive powder particles contain powder Novolac phenol-formaldehyde resin with a content of free phenol of less than about 1 wt.%.

14. Particles according to claim 1, in which the coating contains 1, 2, 3 or 4 layers.

15. Particles according to claim 1, in which the coating further comprises an inorganic and/or inert organic particles.

16. Particles according to claim 1, having an apparent density of from about 1 to about 2 g/cm3and bulk density of less than or equal to approx the RNO 1.0 g/cm 3solubility in acid less than or equal to about 6 wt.%, roundness from about 0.7 to about 0.9, the sphericity of from about 0.7 to about 0.9, and the percentage in the test crushing less than or equal to about 6% at about 16.9 MPa.

17. Particles according to claim 1, in which the substrate is characterized by a solubility in the acid less than or equal to about 6 wt.%, roundness from about 0.7 to about 0.9, sphericity from about 0.7 to about 0.9, and the percentage of the test crushing less than or equal to about 6% at about 16.9 MPa when tested on crushing according to API RP 60.

18. The particle according to claim 1, in which the liquid particles of the composite particles and particles of hybrid filler particles contain silica flour with an average particle size of less than or equal to about 20 microns.

19. The proppant containing particles according to claim 1.

20. Particles of gravel packing containing particles according to claim 1.

21. Particles foundry containing particles according to claim 1.

22. The method of obtaining engineering particles coated with a size of from about 5 to about 200 mesh containing the substrate and on the substrate coating, which, in turn, contains a continuous phase containing curable rezol phenol-formaldehyde resin, and a reactive powder particles embedded in C is eryou phase or bonded thereto, which includes stages:
mixture at a temperature of from about 10 to about 65°With the substrate with a liquid coating material from curing rezol phenol-formaldehyde resin with the formation of the resin cured coatings in the form of continuous phase on a substrate, where the substrate is selected from the group consisting of:
particle-substrate containing an inorganic material and, optionally, at least partially utverjdenie resin coating,
particle-substrate containing an organic material and, optionally, at least partially utverjdenie resin coating,
composite particles containing essentially homogeneous molded part containing the first portion of binder, and filler particles dispersed throughout the mentioned first portion of a binder where the specified first portion at least partially overiden, and where the size of the filler particles ranges from about 0.5 to about 60 μm; and
hybrid particle containing composition layer, located on the inorganic core particle, and a composite layer contains at least partially utverjdenie organic coating and filler particles, and the size of the filler particles ranges from about 0.5 to about 60 μm; and
where the coating contains a curable rezol finalf maldehyde resin;
the mixture of reactive powder particles covered with the resin substrate with the aim to implement them in nepreryvnuyu phase resin coating or glue to it, resulting in a gain engineering particles.

23. The method according to item 22, in which the reactive powder particles contain at least one component selected from the group consisting of rezol phenol-formaldehyde resin, phenol-formaldehyde Novolac resin of ester, acrylic compounds and urethane.

24. The method according to item 23, in which the reactive powder particles are mixed with the particle-substrate at a temperature in the range from about 10 to about 50°C.

25. The method according to item 22, in which the reactive powder particles are mixed with the particle-substrate at a temperature in the range from about 10 to about 50°C.

26. The method according to item 22, in which the substrate has a particle size in the range from 6 to 100 mesh.

27. The method according to item 22, in which the substrate has a particle size in the range from 12 to 80 mesh.

28. The method according to item 22, in which the reactive powder particles have an average particle size of about 100 mesh or less.

29. The method according to item 22, in which the reactive powder particles have an average particle size of about 200 mesh or less.

30. The method according to item 22, in which the coated particle characteristics is : the loss of mass on ignition of from about 0.3 to about 5 wt.%, attributed to the coating on the substrate.

31. The method according to item 22, in which the substrate is a particle-substrate containing an inorganic material and which is characterized by weight loss on ignition of from about 0.3 to about 5 wt.%, attributed to the coating on the substrate.

32. The method according to item 22, in which the substrate is a particle-substrate containing an organic material and which is characterized by weight loss on ignition of from about 0.3 to about 8 wt.%, attributed to the coating on the substrate.

33. The method according to item 22, in which the substrate is a composite particle.

34. The method according to item 22, in which the substrate is a composite particle, and the coated particle is characterized by loss of weight on ignition of from about 10 to about 20 wt.%.

35. The method according to item 22, in which the substrate is a hybrid particle.

36. The method according to item 22, in which rezol phenol-formaldehyde resin continuous phase contains free formaldehyde in the amount of less than about 3 wt.%.

37. The method according to item 22, in which the reactive powder particles contain powder rezol phenol-formaldehyde resin with a content of free formaldehyde is less than about 3 wt.%.

38. The method according to item 22, in which the reactive powder particles contain powder is volacno phenol-formaldehyde resin with a content of free phenol of less than about 1 wt.%.

39. The method according to item 22, which put the first layer of cured coatings of rezol phenol-formaldehyde resin, then the first quantity of reactive powder particles, and then put the second layer of cured coatings of rezol phenol-formaldehyde resin and then the second quantity of reactive powder particles.

40. The method according to item 22, in which the reactive powder particles contain inorganic and/or inert organic particles.

41. Method of treatment of a subterranean formation comprising pumping the fluid for fracturing in a subterranean formation where the fluid contains particles according to claim 1, and heat the subterranean formation particles for curing curable coating particles inside an underground reservoir.

42. The method of forming a gravel packing, including:
the suspension of the particles according to claim 1 with the formation of the suspension,
pumping the slurry into the well and
drainage of the carrier fluid with the formation of gravel packing.

43. The method according to item 22, in which the coating of the curable liquid rezol phenol-formaldehyde resin is applied onto the substrate, and thereafter the operation of mixing for a sufficient time to form on the substrate in a continuous phase of the resin cured coatings with subsequent primitivni the m reactive powder particles in sufficient time for mixing of the reactive powder particles covered with the resin substrate, resulting in getting dry evenly coated particles, which are stored engineering without noticeable stickiness.



 

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SUBSTANCE: proposed fluid to be used in oil fields comprises: 0.001 wt % to 0.5 wt % of surfactant reducing drag and at least one activator of drag reduction selected from the following group: polymer drag reduction activators selected from the group comprising low-molecular water-soluble polymers and copolymers containing at least one aromatic cycle, or their mixes with monomer drag reduction activator. Note here that said fluid allows drag reduction percentage making at least 20%. Proposed method of regulating clay swell in brine-free well shaft comprises: preparing above fluid suspending reduction agent and injecting it into well shaft. Method of processing in-situ in oil filed whereat said suspending reduction agent is prepared, injected into well shaft to reach drag reduction percentage equal to at least 20%. Invention is developed in dependent claims.

EFFECT: improved viscosity and power to suspend solid substances at low surfactant concentrations.

20 cl, 33 ex, 4 tbl, 36 dwg

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2 ex

FIELD: gas and oil production.

SUBSTANCE: water composition for reservoir hydraulic fracturing contains water, ion-bound gel-like system including charged polymer, oppositely charged foaming agent and gas. The gel-like system and gas are present in amount sufficient for production of ion-bound foamed composition for hydraulic fracturing. Composition contains liquid for hydraulic fracturing including 5.5-7 gpt of the above said gel-like system and de-ionised water. The procedure for production of foamed compositions consists in production of the first composition, the second composition and in adding it to the first one at their specified ratio. The procedure for reservoir hydraulic fracturing includes production of liquid for hydraulic fracturing containing the above said gel-like system and proppant and in its pumping into the reservoir. The procedure for reservoir hydraulic fracturing includes production of liquid for hydraulic fracturing containing the above said gel-like system, its pumping into the reservoir at pressure of hydraulic fracturing and in pumping proppant after hydraulic fracture.

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45 cl, 1 tbl

FIELD: gas and oil production.

SUBSTANCE: procedure for treatment of underground formation with processing thickened liquid consists in: mixing water, carbonyl containing first compound and amine containing second compound. The carbonyl containing first compound contains at least one carbonyl group and corresponds to either gel forming agent or to modifying agent. The amine containing second compound contains at least one amine group and corresponds to a gel forming agent when the carbonyl containing first compound is a modifying agent, and to a modifying agent when the carbonyl containing first compound corresponds to the gel forming agent. The gel forming agent corresponds to at least one following compounds: polysaccharide, natural polymer, bio-polymer or synthetic polymer and the modifying agent corresponds to at least one of the following compounds: halogenide, epoxide, polysaccharide, natural polymer, bio-polymer or synthetic polymer. Further, the procedure consists in interaction between at least one carbonyl group of the first compound and at least one amine group of the second compound with formation of modifying bond and production of the modified gel forming agent and in introduction or thickened liquid into a section of an underground formation. The procedure for formation of break of a section of the underground formation by means of processing thickened liquid includes the above said stages. Also, processing thickened liquid is pumped into a section of the underground formation under pressure sufficient for creation or expansion of at least one break in it.

EFFECT: production of modified thickened agents.

16 cl

FIELD: gas and oil production.

SUBSTANCE: procedure for preparing propping agent with coating consists in application of coating on surface of granule. Coating consists of binding and fibre, part of which projects beyond borders of a binding layer. Ratio between length of each fibre and diametre of granule is from 0.06 to 0.44. Additionally, there is carried out treatment with silicon-organic or fluoric-carbon oil-wetting agent at amount from 0.5 to 10% of fibre weight. Propping agent is prepared by the above described procedure. The invention is developed in dependent points of formula.

EFFECT: reduced water-cut of hydrocarbon raw stock at operation of well.

9 cl, 8 ex, 1 tbl

FIELD: oil and gas production.

SUBSTANCE: procedure for stimulation and stabilisation of region of underground bed consists in: delivery of acidulous liquid into region of underground bed and allowing acid, at least partially, to dissolve part of region of underground bed, in pumping cementing liquid containing agent increasing stickiness and including water stickiness increasing agent, in delivery of liquid for successive flushing into region of underground bed and in pumping replacing liquid into underground bed directly upon stage of delivery of acidulous liquid into region of underground bed.

EFFECT: increase and maintaining well output.

55 cl

Deflecting fluid // 2433157

FIELD: mining.

SUBSTANCE: deflecting fluid for temporary sealing of the upper and lower parts of a treated interval in an underground formation by means of supply of the deflecting fluid into holes defined by a drill hole, being hydraulically connected with the treated interval, besides, the deflecting fluid includes a water bearing fluid, which substantially contains water, where particles of the first deflecting agent and particles of the second deflecting agents are dispersed, where the particles of each of the first and second deflecting agents include particles of the propping agent substrate, having a water-soluble polymer coating, besides, the particles of the first deflecting agent have density, which is higher than the density of the water bearing fluid, while the particles of the second deflecting agent have the density, which is less than the density of the water bearing fluid, where the water-soluble polymers of each of the first and second deflecting agents are independently selected from the group that consists of collagen of type I, collagen of type II, collagen of type III, collagen of type IV, collagen of type V and their mixtures. The method to prepare the treated interval in the underground formation for formation fracturing to increase intensification of flow from the treated interval by means of formation fracturing, includes injection of the above specified deflecting fluid into the treated interval, which results in the fact that the particles of the first deflecting agent are deposited in the lower part of the treated interval, forming a temporary lower border, which substantially seals the lower part of the treated interval relative to the flow of liquid via this lower border, and the particles of the second deflecting agent rise in the upper part of the treated interval, forming a temporary upper border, which substantially seals the upper part of the treated interval relative to the flow of liquid through this upper border.

EFFECT: intensification of flow into one or many intervals in underground drill holes as a result of deflection of working fluids flow to process a drill hole in a certain direction.

16 cl, 2 ex, 3 dwg

FIELD: oil and gas production.

SUBSTANCE: spherical ceramic propping filler designed for oil or gas wells hydraulic fracturing is characterised with recesses on its surface. The procedure for forming recesses on surface of spherical ceramic propping filler consists in stages of drying, crumbling and granulation of raw stock with a successive stage of granulated material sintering. Also, the procedure does not include stages of calcination before the said stage of granulation. Here is also disclosed the procedure for oil or gas wells hydraulic fracturing where the above described propping filler is used as propping filler for hydraulic fracturing. The invention is developed in dependent points of formula.

EFFECT: raised efficiency of extraction of oil or gas from wells.

13 cl, 4 tbl, 7 dwg

FIELD: mining.

SUBSTANCE: using a composition of a sealant emulsion to reduce diagenesis of mineral surface in an underground layer, where the composition of the sealant emulsion contains a water fluid; a surfactant and a sealant, at the same time the specified emulsion has a water external phase and an oil internal phase, the sealant is a non-water additive, which gives stickiness, selected from a group that contains of polyamides, polyesters, polycarbonates, polycarbamates, natural resins and their combinations, or resin selected from a group made of a double-component resin on the epoxide basis, resins on the basis of furans, phenol-based resins and resins on the basis of phenol/phenol-formaldehyde/furfuryl alcohol, besides, the composition of the sealant emulsion is introduced into the underground layer, and multiple particles are coated with a sealant emulsion to produce multiple particles coated with a sealant emulsion. The invention is developed in the formula subclaims.

EFFECT: facilitation of works performance, transportation and cleaning.

6 cl, 3 dwg, 2 ex, 1 tbl

FIELD: oil and gas production.

SUBSTANCE: modifier reducing time for recovery upon effect of shearing force of liquid medium on base of viscoelastic surface-active substance for process treatment of underground bed of deposit corresponds to fibrous substance or substance in form of particles, or their mixture in concentration sufficient for time of recovery upon effect of shearing force equal to 60 seconds or less, where concentration amounts to approximately 0.0001% to approximately 5 % wt of total weight of liquid medium. The inventions are developed in dependent points.

EFFECT: facilitation of time for recovery of fluid medium upon effect of shear force equal to 60 seconds or less.

20 cl, 1 tbl

FIELD: oil-and-gas production.

SUBSTANCE: proposed fluid to be used in oil fields comprises: 0.001 wt % to 0.5 wt % of surfactant reducing drag and at least one activator of drag reduction selected from the following group: polymer drag reduction activators selected from the group comprising low-molecular water-soluble polymers and copolymers containing at least one aromatic cycle, or their mixes with monomer drag reduction activator. Note here that said fluid allows drag reduction percentage making at least 20%. Proposed method of regulating clay swell in brine-free well shaft comprises: preparing above fluid suspending reduction agent and injecting it into well shaft. Method of processing in-situ in oil filed whereat said suspending reduction agent is prepared, injected into well shaft to reach drag reduction percentage equal to at least 20%. Invention is developed in dependent claims.

EFFECT: improved viscosity and power to suspend solid substances at low surfactant concentrations.

20 cl, 33 ex, 4 tbl, 36 dwg

FIELD: oil-and-gas production.

SUBSTANCE: proposed composition comprises surfactant, i.e. organic residue of ammonium sulphate production from waste sulphuric acid produced in sulphuric-acid alkylation of isoalkanes with olefins in amount of 2-10 wt %, water making the rest.

EFFECT: availability and low costs, high oil-sweeping property.

1 ex, 1 tbl

FIELD: oil and gas industry.

SUBSTANCE: insulation method of water influx to production oil wells involves pumping of gel-forming compound prepared by introducing the carbamide to polymer-colloidal complex obtained by mixing of water colloidal solution of aluminium pentahydroxochloride with 0.2÷0.3 wt % of water solution of polymer; at that, as polymer there used is weakly charged cationic polyelectrolyte with molecular weight of 6·106-20·106 and content of cationic groups of 1.65 to 9.20% molar.

EFFECT: increasing oil production owing to reducing water content of extracted products.

4 tbl, 5 ex, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: as per the first version the drilling fluid contains the following, wt %: PBMA bentonite 6.0-7.0; sodium carbonate 0.1÷2.0; sodium hydroxide 0.1-0.5; Givpan 0.2-0.3; Kamtsel polyanionic cellulose PATs-VV 0.1-0.3; Lubriol lubricant 1.0; acrylate lignosulphonate reagent ALS 0.2-0.3; antifoaming agent - 10% suspension of polyethylene in solar oil or kerosene PES 0.1-0.2. As per the second version the drilling fluid contains the following, wt %: PBMA bentonite 5.0-6.0; sodium carbonate 0.1÷2.0; sodium hydroxide 0.1-0.5; Givpan 0.2-0.3; Kamtsel polyanionic cellulose PATs-VV 0.1-0.3; Kamtsel polyanionic cellulose PATs-SV 0.1-0.3; Lubriol 1.0; ALS 0.2-0.3; polyethyl siloxane fluid (PSF) 0.1-0.2. As per the third version the drilling fluid contains the following, wt %: PBMA bentonite 2.0; sodium carbonate 0.1÷0.5; sodium hydroxide 0.1÷0.5; Kamtsel polyanionic cellulose PATs-VV 2.0; Kamtsel polyanionic cellulose PATs-SV 2.0; ALS 0.2÷0.3; xanthan gum 0.1.

EFFECT: possibility of failure-free drilling of controlled directional wells in complicated mining and geological conditions.

3 cl, 6 tbl, 3 ex

FIELD: oil and gas industry.

SUBSTANCE: polymer-clay drilling fluid in permafrost and highly colloidal clay rocks includes the following, wt %: clay powder - 1.000-3.000, Robus KK biopolymer - 0.300-0.100, Na CMC (carboxymethyl cellulose) - 0.200-0.300, Praestol 2530 - 0.010-0.015, water-repellent fluid "Osnova-GS" - 0.200-0.300, lubricant KSD - 1.000-1.500, water - 97.290-94.785, carbonate weighting material - 37.000-0.000 plus 100, barite weighting material - 14.000-62.000 plus 100.

EFFECT: providing pseudoplastic properties and controlled density of polymer-clay fluid.

1 tbl

FIELD: oil and gas industry.

SUBSTANCE: clay-free drilling fluid for completion of formations of controlled directional and horizontal wells in conditions of abnormally high formation pressures involves the following, wt %: potash or sodium formiate 10.0-50.0; Robus KK biopolymer 0.40-0.45; modified KREM amylase 1.0-1.1; water-repellent fluid "Osnova-GS" 0.25-0.30, complex lubricant KSD 1.0-1.5; water 46.65-87.35; marble powder 30-65 plus 100; barite weighting material - up to 65 plus 100.

EFFECT: providing high density of drilling fluid, required carrying-over and retaining capacity, reducing hydraulic resistances at movement, high lubricating and water-repellent properties of drilling fluid for improvement of the operating conditions of rock-destructing tool on working face; simplifying the passage of drilling string and preventing seizures in horizontal well shaft, high inhibiting and colmatation properties, low filtration rate for maintaining the stability of clay rocks forming the walls of the well at maintaining collecting properties of productive formation.

1 tbl, 7 dwg

FIELD: oil and gas industry.

SUBSTANCE: method involves placing into the well interval at the hydraulic fracturing and above it of viscous working liquid with propping agent with fraction of 0.4-0.8 mm in the suspended state; placing in the well above viscous working liquid of process liquid with density of 1.3-2.0 g/cm3 and creation of cracks in the formation by means of viscous working liquid with the energy released during the charge burning. The charge is placed in the viscous working liquid zone. At that, the liquid including the following components per 1 m3 is used as viscous working liquid: biocide "Biolan" - 0.005-0.007 l; gelling agent "GPG-3" - 4-5 kg; borate binding agent "BS-1" - 3-4 l; surface active substance - destruction modifying agent "KhV" - 1-3 l; propping agent - 100-300 kg; water is the rest.

EFFECT: increasing intensification effect of the product inflow from the formation owing to reducing the charge energy losses, increasing the operating safety and improving the effect of stable formation drainage in time.

3 cl, 1 ex

FIELD: mining.

SUBSTANCE: fluid for treatment of wells contains a water-based liquid, a crosslinking agent and a gel-forming agent, containing a crosslinked polymer and a non-crosslinked biopolymer, where a molecule of the latter consists only of glucose or has the main chain, comprising a glucose link and a linear or cyclic monosaccharide link of the specified type, and ratio of a biopolymer to a crosslinked polymer makes 0.05-1:1. The method for treatment of a part of an underground bed includes provision of the above-specified liquid and its injection into a well shaft that penetrates into an underground bed. The above-specified method, where the liquid for treatment comprises a crosslinked polymer and diutan with diutan ratio to crosslinked polymer equal to 0.05-1:1.

EFFECT: improved rheological properties and temperature stability of gel-forming agents.

21 cl, 3 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: anti-agglomerates are surface-active non-quaternary nitrogen-containing compounds with 1-5 nitrogen atoms, which have at least one hydrophobic group with 6-24 carbon atoms, and where the hydrophobic group is bonded to the remainder of the molecule by an amine moiety, an ether moiety or an amide moiety, provided that when the hydrophobic group is bonded by an amide moiety to the remainder of the molecule, the compounds must contain a total of at least two nitrogen atoms, and optionally contain 1-12 -CH2CH2O- groups and/or 1-6 hydroxyalkyl groups with 3-4 carbon atoms; and compounds having at least one C2-C3 acyl group and/or at least one hydroxyalkyl group with 3-4 carbon atoms; or a salt thereof. The method of inhibiting agglomeration of gaseous hydrates in a conduit, containing a fluid mixture which contains hydrocarbons with 1-4 carbon atoms and water, involves adding to the mixture said agglomerate in amount of 0.05-10% of the content of water in the fluid mixture. The composition contains said anti-agglomerate of gaseous hydrates, a corrosion inhibitor and/or a paraffin deposition inhibitor.

EFFECT: high efficiency of the anti-agglomerate for gaseous hydrates and biodegradability thereof.

9 cl, 2 ex, 2 tbl

FIELD: gas and oil production.

SUBSTANCE: quick-setting spacer mix for water and gas flow insulation in low-temperature oil and gas wells, including carbamide-formaldehyde resin, acid solidifier, barite and water, with 2% aqueous solution of nitryltrimethylphosphonic acid as acid solidifier, at the following component ratio, wt %: carbamide-fimraldehyde resin 45.0-50.0, 2% aqueous solution of nitryltrimethylphosphonic acid 2.5-4.5, barite 40.0-49.0, the rest is water. The invention is developed in dependent points of formula.

EFFECT: reduced gas permeability, increased oil recovery from beds, intensified oil production.

3 cl, 2 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to machine building, particularly, to production of carbon-carbon composite material coat. Proposed method comprises applying composition consisting of the mix of borosilicate glass powder and binder on material surface. Prior to applying said composition, material surface is processed by water suspension of fumarole acid in volume ratio of 1:1. Aforesaid binder is made up of composition containing (in wt %): 40-45 - ethyl silicate, 40-45 - ethanol and 10-20 - silicon organic varnish.

EFFECT: protection of composite material at 1000-1200°C for preset service life of aersospace equipment.

1 ex

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