Method of binding non-monolithic oxide inorganic materials by etherified aminoplast resins, hardened compositions from such materials and etherified aminoresins

FIELD: chemistry.

SUBSTANCE: invention relates to method of binding non-monolithic inorganic materials by hardenable compositions, as well as to hardened compositions, which can be obtain by claimed method. Method consists in performing contact of inorganic materials with hardenable composition, which contains, at least, one hardenable etherified carbamide-formaldehyde resin, which contains certain structural units, with further thermal resin hardening. Amount of hardenable composition constitutes from 0.5 to 60 wt % counted per inorganic materials, and hardening is performed at temperature from above 0 to 280°C.

EFFECT: obtained hardened compositions possess improved physical-mechanical characteristics.

10 cl, 11 tbl

 

The present invention relates to a method of binding a non-monolithic inorganic oxide materials curable compositions that contain the esterified resins, as well as to utverzhdennym compositions that can be obtained this way. In a preferred embodiment of the invention it is about the method of stabilizing a subterranean formation of inorganic oxide materials, in accordance with which the curable composition is injected into the subterranean formation and then utverjdayut at prevailing in the formation temperatures.

In exploration drilling of oil and gas in unconsolidated layers of sand and rocks often find hydrocarbons, respectively, a typical mixture of hydrocarbons with water. A mixture of hydrocarbons with water under the action of shear forces arising in the process of extraction of these minerals can take from underground formations of sand particles. The latter may reach, for example, in the production pipelines, underground and surface pumping equipment, as well as in the water separator and piping system, causing corrosion, abrasion and breach or impairment of their normal operation.

In addition, it is known that production wells stimulated by disclosure containing hydrocarbon species (so-called hydraulic fracturing) is Performed while the holes of the support in a production environment over long periods of time in an open condition by placing them in protective materials, for example, such as sand or particles of bauxite. Particles such protective materials can also be made from the cleft to the outside. In addition to the above problems, it is also possible circuit formed in the rock clefts and a corresponding sharp drop in the flow rate used for the extraction of hydrocarbon wells.

In the prior art there are known various methods of preventing sand mixture of hydrocarbons with water from the formation through the production well with the subsequent sand production pipelines and process equipment.

So, for example, to prevent transport of sand from the production well perform its gravel backfill and install mechanical sand filters. Such systems are described, for example, in the patent Canada CA 2314392 and patent applications U.S. US 2008217002 A1.

In addition, unconsolidated sand reservoir can be pumped flowable resin, and then subjecting it to curing. In the case of known prior art systems of this type in the borehole depending on its temperature, you can enter the appropriate hardener, for example, an organic amine. The resin can be injected into the formation together with a hardening agent directly in the form of liquid or applied on the basis of the state, and is used as a base, for example, fine particles of sand. When the volume in the formation sand grains locally glued together with resin, as a result they lose the ability to take away from the reservoir, however, the hydrocarbon retaining the ability to penetrate compacted sand.

Located in a borehole cured resin must maintain long-term stability to hydrolysis at the prevailing temperature field and not subject to dissolve in the extraction of hydrocarbon.

For example, in patents great Britain GB 1172116 and GB 1453001 described using based on furfuryl alcohol resin, which is injected into the formation in the form of a solution in an organic solvent. In the German patent DE 2843452 and patent Canada CA 2637696 described respective systems based on epoxy resins.

The need for binding inorganic particles suitable methods to prevent the exfoliation of the loose rocks at penetration or to protect the breed from weathering, respectively, oxidation, there is also in other branches of engineering, for example, in the mining industry. For example, in the patent Canada CA 2497722 describes the application of two-component elastomeric resins, which are applied to the rock surface, and then implement the process of film formation.

Other examples relate to the prevention of dust formation or hardening of the soil. For example, in the patent RU 2151301 described the prevention of dust generation by the light is ivania dust using polyvinyl butyral and sand.

Considerable technical interest is the hardening of sand in above-ground technical areas. So, for example, with additional use of adhesive materials made of sand moulded products, also known as molds, which are a lot of different ways, including metal casting. In particular, in patent application China CN 1075114 And German patents DE 2400908 and DE 1012035, as well as in Japanese patent application JP 02197348 A2 describes the use of urea-formaldehyde resins for the manufacture of molded products, providing the variation of the molar ratio of urea to formaldehyde, and type of curing agent.

In addition, it is known, about the improvement of engineering properties such molded products through the use of additional additives, for example, furfuryl alcohol (German patent DE 1160141), and the transformation of urea-formaldehyde resins in the sulfonates (Yang, Ming and others, Beijing Huagong Daxue Xuebao, Ziran Kexueban (2003), 30(4), 81-84) or the use of phenolic additives (patent Czechoslovakia CS 247931).

About the strengthening of aboveground and underground sand layers through urea-formaldehyde systems reported in patent applications US US 2006240995 and US 6311773, patent RU 2048950, as well as in U.S. patent US 5670567.

The present invention was based on the task will offer the improved method of binding a non-monolithic inorganic oxide particles, first of all particles of silicon dioxide, using resins that could be used in many different application areas. Thus preferably you should use resin water-based.

In line with this, a method was found to bind non-monolithic inorganic oxide materials, in accordance with which implement the contact of inorganic materials with a curable composition comprising at least one curable resin, and subsequent thermal curing resin, and the resin using esterified to the amino quantity of the curable composition in terms of inorganic material is from 0.5 to 60 wt. -%, and curing is carried out in a temperature range from 0 to 280°C.

In addition, they found solid composition of inorganic particles and utverzhdenii resin, which can produce the above.

In a preferred embodiment of the invention it is about the method of stabilizing a subterranean formation of inorganic oxide materials, and the curable composition is injected into an underground formation and utverjdayut at prevailing in the formation temperatures.

In another embodiment, the present invention relates to solid compositions, which can be obtained by mixing one or more eter is infected amino and one or more hardeners with particles of silicon dioxide, water and/or other solvent and curing the resulting mixture at room or elevated temperature.

In accordance with another variant of the present invention relates to the use of esterified amino, and one or more curing agents for the manufacture of water-resistant solid sand compositions.

The present invention is implemented, in particular, as follows.

For carrying out the invention use a curable composition, which contains at least one esterified to amino.

Ameloblastoma in principle known in the art. These relatively low molecular weight polycondensation products containing NH-groups of compounds with carbonyl compounds. Examples of suitable compounds containing NH-groups are urea, melamine, urethanes or aromatic amines. Suitable carbonyl compound is preferably formaldehyde, but it can be also of higher aldehydes or ketones.

Esterified aminoplasmal also in principle known in the art. Such resins are obtained by complete or partial tarifitsirovana hydroxyl groups, amino alcohols. Suitable alcohols are primarily monohydroxy aliphatic alcohols with 1-10 carbon atoms, preferably of aliphati the definition monohydroxy alcohols with 1-4 carbon atoms, and diatomic alcohols with 1-10 carbon atoms. Examples of such alcohols are methanol, ethanol, butanol, 1,2-ethanediol or 1,4-butanediol. Preferably, you can use the esterified resins containing urethane groups. Such resins can be obtained, due to at least partial use for the esterification of diatomic alcohols with 1-10 carbon atoms or by subsequent transesterification esterified with monohydroxy alcohols connections with diatomic alcohols. Esterified aminoplasmal are commercially available products.

Additionally, the esterified aminoplasmal you can optionally modify the appropriate additives. Examples of suitable additives are 3-aminopropyltrimethoxysilane, 3-amino-propyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, polytetrahydrofuran or phenol-formaldehyde resin.

For the target application aminoplasmal and esterified aminoplasmal can be cured to the corresponding reactive layer. As a rule, in this case, use a curing agent, preferably an acid curing agent, although the use of hardeners is not always required. Suitable hardeners aminoplasmal known in the art. Examples of suitable hardeners t is Auda inorganic or organic acids and/or their salts. Relevant examples are ammonium chloride, ammonium nitrate or maleic acid. Obviously, you can also use a mixture of two or more hardeners.

In a preferred embodiment of the invention under esterified aminoplasmal mean etherified urea-formaldehyde resins. Such resins are produced by the interaction of urea with formaldehyde and subsequent esterification products of this interaction. Etherified urea-formaldehyde resins are commercially available products.

Preferred etherified urea-formaldehyde resins that contain structural units of the General formula (I) and/or (II):

,

,

moreover, the residues R1, R2, R3 and R4 denote substituents selected from the group comprising hydrogen, -CH2HE-CH2-OR', provided that at least one of the residues R1, R2, R3, and R4 means a group-CH2-OR'.

The substituent R' in the above formula means an aliphatic hydrocarbon residue with 1-10 carbon atoms, above all the rest with 1-4 carbon atoms. The substituent R' is preferably methyl, ethyl or n-botilony residue, particularly preferably methyl or n-botilony the rest.

The coefficient of "x" in the formula (I) denotes a number from 2 to 8, preferably 4, the ratio "y" is a number from 1 to 20, preferably from 1 to 10.

The compounds of formula (I) receive, through the interaction of urea with formaldehyde, and at least one aliphatic monohydroxy alcohol with 1-10 carbon atoms, preferably 1-4 carbon atoms, known in the art conditions. The compounds of formula (II) can preferably be obtained by an additional interaction of the compounds of formula (I) with diatomic alcohol of General formula (III):

.

This reaction is also referred to as carbonatization. Specified diatomic alcohol, obviously, can also be used for the esterification of from the very beginning. It is preferable diatomic alcohols include 1,4-butanediol, and polytetrahydrofuran with an average degree of polymerization in the range from 1 to 20, preferably from 1 to 10.

As is well known to experts in the field of polycondensation reactions, the result of the above transformations get a mixture of different compounds of formula (I), respectively (II). In addition, this mixture can optionally contain neprevyshenie urea. This mixture, as a rule, can be used without further purification, however, can also be pre-targeted selection of compounds with quite is definitely the formula (I), respectively (II).

To obtain etherified urea-formaldehyde resins, urea and formaldehyde used in a molar ratio of from 1:1 to 1:4. The molar ratio used for the esterification of monohydroxy alcohol to the initial formaldehyde is preferably from 0.1:1 to 1:1. If necessary, diatomic alcohol can be used in a molar ratio to urea in the range from 0.1:1 to 0.7:1. The following table outlines the typical and preferred molar ratio of the reactants.

UreaFormaldehydeMonohydroxy alcoholDiatomic alcohol
Minimum110,1optional 0,1
Max144optional 0,7
Preferably, theMinimum11,5 0,50,1
Max13,01,90,5
Particularly preferablyMinimum11,70,50,35
Max12,51,20,55

For the implementation of the present invention preferably use etherified urea-formaldehyde resins that contain structural units of the compounds of General formula (II), i.e. compounds synthesized using diatomic alcohols. In accordance with these etherified urea-formaldehyde resins containing urethane groups, which are also called carbamodithioate resins.

Obviously, you can also use a mixture of two or more different etherified urea-formaldehyde resins. In addition, etherified urea-formaldehyde resins, if necessary, you can also use other curable resin. The number of esterified ka is lamido-formaldehyde resins in such mixtures should be 50% of the mass, preferably at least 75 wt. -%, especially preferably at least 90% of the mass. in terms of the amount of all resins used, and even more preferably as a resin to be used only etherified urea-formaldehyde resins. Examples of other thermosetting resins are phenol-formaldehyde resin, melamine-formaldehyde resin etherified melamine-formaldehyde resin or melamine urea formaldehyde resin.

According to the invention esterified aminoplasmal primarily etherified urea-formaldehyde resins, can be used as such, i.e. without an additional solvent. However, these resins can also be used in dissolved or dispergirovannom in a suitable solvent condition. In relation to the type of solvents do not exist any fundamental restrictions, provided that the resins are sufficiently can be dissolved, respectively dispersed in them. Suitable solvents primarily include water and polar organic solvents, especially organic solvents, able to mix with water. Examples of suitable solvents are water, methanol, ethanol, n-propanol, isopropanol, n-butanol and Isobutanol. Especially prefer inim solvent is water. The resin concentration in the solution can be defined depending on the specific purpose solution.

In addition, used according to the invention esterified aminoplasmal primarily etherified urea-formaldehyde resin, may contain additional additives. Examples of suitable additional additives are silanes or siloxanes, diamines, dicarboxylic acids, diols, polyols or simple politicaly. Examples of suitable additives are butanediol, diethylene glycol, triethylene glycol, polyethylene glycols, Brednikova molecular mass (Mn) preferably does not exceed 1000 g/mol, polytetrahydrofuran, Brednikova molecular mass (Mn) preferably does not exceed 1000 g/mol, or glycerol, in particular, 3-aminopropyltrimethoxysilane, 3 aminopropyltriethoxysilane-silane or (3-glycidoxypropyl)trimethoxysilane. In the presence of such additives mass number usually ranges from 1 to 20 wt%. in terms of the total amount of resins. The quantity of additives experts determined depending on the desired properties.

For curing esterified aminoplasmal primarily etherified urea-formaldehyde resins, curable compositions in principle, you can usually use the s, well-known specialists hardeners, although the use of a separate curing and is not always required. From adding a separate hardener can be waived primarily at temperatures above 100°C, while at temperatures below 100°With his presence, as a rule, is necessary or at least preferable. Examples of suitable hardeners are primarily acidic hardeners, in particular, inorganic or organic acids and/or their salts, such as maleic acid, respectively, maleic anhydride, n-toluensulfonate, methanesulfonate, formic acid, phosphoric acid, ammonium chloride, ammonium bromide, ammonium nitrate, ammonium phosphate or ammonium sulfate. Obviously, you can also use a mixture of two or more hardeners. The use of mixtures of two different hardeners justifies itself first of all in the case, if the staple amenomori should be carried out at low temperatures, e.g. at temperatures from 15 to 40°C. the Type and amount of hardener specialists choose depending on the desired properties of the curable composition. The required speed of curing experts can determine, for example, by varying the amount of hardener used. When using hardener quantity in PE is eschete the resin is from 0.1 to 20 wt. -%, preferably from 0.1 to 10% of the mass.

Especially preferred are combinations of curing agents, including acid, especially maleic acid, respectively, maleic anhydride, n-toluensulfonate, methanesulfonate, formic acid or phosphoric acid, and ammonium salt, especially ammonium chloride, ammonium bromide, ammonium nitrate, ammonium phosphate or ammonium sulfate. The mass ratio of specific hardener in such combinations can be from 1:9 to 9:1, preferably from 1:4 to 4:1, particularly preferably about 1:1. Especially preferred are the following combinations of hardeners: maleic anhydride/ammonium nitrate, maleic anhydride/ammonium sulphate, maleic anhydride/ammonium phosphate, maleic anhydride/ammonium bromide, phosphoric acid/ammonium nitrate, phosphoric acid/ammonium sulfate, phosphoric acid/ammonium phosphate, phosphoric acid/ammonium bromide, methanesulphonate/ammonium nitrate, metasolv-acid/ammonium sulfate, methanesulfonate/ammonium phosphate, methane-acid/ammonium bromide, formic acid/ammonium nitrate, formic acid/ammonium sulfate, formic acid/ammonium phosphate, as well as formic acid/ammonium bromide.

Proposed in the invention curable compositions, which consist of resins, as well as when you want the tees to be used hardeners, and other components, according to the invention is used to bind a non-monolithic oxide inorganic materials, preferably inorganic oxide particles. The formation of solid compositions which contain utverzhdennuyu resin, and a non-monolithic inorganic oxide materials, preferably inorganic oxide particles.

Under "inorganic oxide materials according to the invention involve inorganic oxide materials of any type, it is also about the materials with hydroxyl groups. Such inorganic materials can be of natural origin or may be synthetically derived materials. Examples of inorganic oxide materials are silicon dioxide and silicates, for example, silicate minerals such as quartz, feldspars, silicates, clays or layered silicates. In addition, it may be, for example, oxides, respectively, the hydroxides of aluminum, such as bauxite or aluminates. To oxidic inorganic materials, obviously, should also include a mixture of different materials.

The definition of "non-monolithic", on the one hand, used to refer to materials consisting of inorganic oxide particles. It is, for example, loose coarse-grained oxide inorganic materials, n is the sample, such as sand, gravel or stones, and fine powders of inorganic oxide materials, such as pigments.

Oxide inorganic particles according to the invention have a size generally less than 20 mm, preferably less than 5 mm, but their sizes are not limited to the specified values. The above figures were determined by sieve analysis. Thus, they do not necessarily refer only to primary particles, and can also apply to the agglomerates comprising particles of a smaller size. Preferably it is possible to use particles whose size ranges from 0.01 mm to 2 mm, particularly preferably from 0.1 to 1 mm. Professionals it is clear that these values are average values of particle size. A mixture of different particles, obviously, may also have a bimodal or multimodal size distribution.

For the implementation of the present invention preferably can be used particles of silicon dioxide, primarily sand, especially sand size particles in the approximate range from 0.1 to 1.3 mm, the Degree of purity of the particles of silicon dioxide is preferably from 80 to 100% of the mass. in terms of the total number of particles of silicon dioxide and impurities. In this case, the impurities implies, for example, particles of feldspars or CH is us.

According to the invention under "non-monolithic materials include inorganic oxide materials, which may have pores, cracks, fractures or fissures. Examples of such materials can serve formations, which contain pores, cracks or crevices. Although such formations usually macroscopically and look like a solid education, but the presence of pores, cracks, fissures or clefts can often have a significant negative impact on their stability.

For the implementation of the present invention implement contact the above curable composition containing the resin, and if necessary, present hardeners and other components with a non-monolithic inorganic oxide materials. The nature of the implemented contact is determined by the ordering of the oxide inorganic materials subject to binding by means of resin.

If the associate loose bulk layer of inorganic oxide particles, they can simply be mixed with the curable composition, if necessary, using the appropriate mixing equipment. The resulting mixture can then be molded to give the desired shape and subjected to curing.

If it comes to being in a stationary state in particular the place non-monolithic oxide inorganic material or inorganic oxide particles, for example, sand seams, gravel roads, subject to drilling subterranean formations or be drilling loose solid materials from sand or other inorganic oxide particles, the use of mixing equipment, for obvious reasons, is not possible. In such cases, the cured composition should either be sprayed on the subject of strengthening material, or pumping inside to be strengthening material.

The amount of the curable composition to be used for binding particles, specialists set depending on the required properties of a solid composition consisting of utverzhdenii resin and inorganic oxide particles. It is determined, for example, the required strength of the final material. The optimum amount of resin in terms of inorganic oxide particles is from 0.5 to 60 wt. -%, first of all, from 1 to 40 wt. -%, preferably from 2 to 25 wt. -%, particularly preferably from 3 to 15% of the mass.

Then for the purpose of binding a non-monolithic, inorganic oxide materials curable resin is subjected to curing, which is carried out at temperatures of from more than 0 to 280°C, preferably from 5 to 200°C., particularly preferably from 10 to 180°C. the Curing of the resin is also determined by the arrangement are subject to binding oxide neorg the organic particles. For example, mobile moulded products with the aim of curing can be heated in an appropriate furnace. When the curing temperature should correspond to the chemical nature of the hardener. In the case of stationary ordered in a certain place of the non-monolithic inorganic oxide materials, the curing temperature, as a rule, automatically determined by prevailing in a particular place temperature, for example, the temperature inside the subterranean sand formation. However, in the presence of appropriate technical capabilities of specialists can also submit necessary for curing the heat inside such fixed formations.

Proposed in the invention method can be used to associate a non-monolithic inorganic oxide particles of different types with different character ordering.

So, for example, proposed in the invention method can be used for manufacturing molded products of the inorganic oxide particles, preferably of silicon dioxide, respectively, of the sand. Additionally, proposed by the invention method can be hardening, for example, the seams of sand, construction pits, roads or rock, and the method is also suitable for use in tunneling.

Proposed in the invention method the person is but preferably can be used in the oil and gas industry. For example, it can be used to bind sand formations through which carry out the drilling. To this end the above-mentioned curable composition is injected into unconsolidated subterranean sand formation and expose it to cure.

The sequence of process operations can include, for example, that after the drilling of wells in the sandy layer (if the well has not been drilled previously) curing the composition by means of pumps pump to be treated formation. In this case, as a rule, are used depending on the type of the corresponding curable resin composition which additionally contains at least one solvent, preferably water. The concentration of resin in the curable composition should be set so that generated by hydraulic pumps pressure was sufficient to pump a specified composition in the subject hardening formation and its extensive penetration into the formation. Therefore, such use is particularly suitable curable composition, a viscosity, measured at 25°C. is not more than 30 MPa·s, preferably not more than 10 MPa·S. the concentration of the resin in such curable compositions typically ranges from 5 to 50 wt%. in terms of the sum of all components is s-curable composition.

In the case of use in the curable composition of the hardener before the introduction of the composition into the formation of the hardener is mixed with the resin. The type and amount of curing agent should be selected so that the binding resin occurred only after penetration of the curable composition into the formation. Depending on the nature of the formation stitching, usually begins after a period of time after contact curable compositions 1 to 6 hours.

Loss of reinforcement materials after stimulation can be prevented due to the fact that the injection proposed in the invention compositions is carried out after the installation of the reinforcing material in the cleft, which is then curing uploaded songs. The resin cures in the cleft and, therefore, prevents the extrusion of the protective material from crevices during the production of hydrocarbons.

Another field of application of the invention method is the mining industry where it is used to prevent the movement of loose rock in places penetrations or to protect the breed from weathering, respectively oxidation.

In addition, the proposed in the invention method can be used to prevent dust emission, for soil stabilisation, for example, mining is promyshlennosti, and when surfacing neapolitani roads.

Used according to the invention esterified aminoplasmal primarily etherified urea-formaldehyde resins, have several advantages compared to neeterificirovannah systems. For example, they have a much higher resistance to water, salts and organic solvents, which makes it particularly optimal way to solve problems arising in the area of oil and natural gas in contact with (salt-containing) water and hydrocarbons.

Urea-formaldehyde resin etherified short-chain alcohols, especially methanol, possess sufficient solubility in water, so they can be used in a technically appropriate concentrations. With the direct application of such curable compositions can be waived from the addition of organic solvents and use water instead.

In addition, it was found that the curing system based acids allow for precise time setting proposed in the invention curable compositions, which, as a rule, it is necessary for underground use.

The following examples serve for a more detailed explanation of the present invention.

1. is erva series of experiments

In the first series of experiments used the following market esterified aminoplasmal.

Resin 1 Market melamine-formaldehyde resin with a high degree of tarifitsirovana with methanol, dissolved in a mixture of methanol with water (approximate solids content from 81 to 85 wt. -%).

Resin 2 Market esterified with methanol, carbonateserophene, containing structural units of the formula (II), urea-formaldehyde resin (no solvent).

Resin 3 Market esterified with methanol, carbonateserophene urea-formaldehyde resin in aqueous solution with an approximate solids content of from 75 to 79% of the mass.

Resin 4 Market esterified with methanol, decarbonatization urea-formaldehyde resin in aqueous solution with an approximate solids content of from 75 to 79% of the mass.

Modified resin

In addition, receive a modified resin additives. To this end each of the resins 1-4 are mixed with an appropriate additive, and the resulting mixture is heated for two hours at a temperature of 80°C and pH in the range from 7 to 8. Additives used and their quantity (mass ratio) shown in table 1.

The manufacture of hardened sand compositions (General statement)

8 g correspond to the her resin is mixed with 0.24 g of the corresponding hardener. To the resulting mixture add sand with an approximate particle size of from 0.3 to 0.8 mm, and the components are mixed. The mixture is subjected to extrusion in the form and cured overnight at 57°C. Then utverzhdennuyu composition extracted from the form and used for subsequent tests. The obtained molded product has a size of 8 cm × 1 cm × 0.5 cm Corresponding to the source of the resin and hardeners described in table 1.

Tests in terms of technical application

Using obtained as described above, samples, perform the following tests.

The appearance and durability

Perform a qualitative evaluation of the appearance and strength of the respective molded products.

Water resistance

To determine the water resistance of the samples incubated for 2 hours in water at a temperature of 80°C and then dried (phase 1). After soaking in the water again qualitatively evaluate the appearance and strength of molded products. However first of all it is important to install, did the moldings specified test or collapsed.

Then the samples (if possible) again stand in water for 20 days at room temperature (phase 2).

After that, the samples within two months aged in water at 80°C and mark the onset of their destruction (phase 3).

The results of the respective tests are shown in table 1./p>

Elasticity

In addition, determine the mechanical properties of molded articles (Flexural strength and strain at break). The corresponding measurements are performed according to ISO 178, using samples with dimensions of 80 mm × 10 mm × 5 mm, the distance between the contact points when the dimension is 64 mm, a bending speed of 2 mm/min, measurements are performed at room temperature.

Characteristics of the respective samples and the measurement results are shown in table 2.

Table 1
The composition of the solidified sand compositions and their resistance
Number exampleResinThe hardenerAppearance after demoldingWater resistance
Phase 1Phase 2Phase 3
I-1Resin 1NH4ClGood---
I-2Smola NH4NO3Good---
I-3Resin 1Maleic acidGoodGoodGood1 day
I-4Resin 2NH4ClGoodGoodGood>2 months
I-5Resin 2NH4NO3GoodGoodGood>2 months
I-6Resin 2Maleic acidGood---
I-7Resin 2+ 3-aminopropyltriethoxysilane (1:0,11)NH4ClGood GoodGood>2 months
I-8Resin 2+ 3-aminopropyltrimethoxysilane (1:0,05)NH4ClGoodGoodGood>2 months
I-9Resin 2+ 3-aminopropyltrimethoxysilane (1:0,05)NH4NO3GoodGoodGood>2 months
I-10Resin 3+ 3-aminopropyltrimethoxysilane (1:0,05)NH4ClGoodGoodGood>2 months
I-11Resin 3+ 3-aminopropyltrimethoxysilane (1:0,05)NH4NO3GoodGoodGood>2 months
I-12Resin 3+ 3-aminopropyltriethoxysilane (1:0,13) NH4ClGoodGoodGood1 day
I-13Resin 4+ ethylene glycol (1:0,6)Maleic acidGoodGoodGood1 day
I-14Resin 4 +3-aminopropyltriethoxysilane (1:0,6)Maleic acidGoodGoodGood1 day
I-15Resin 2+ phenol-formaldehyde resin (1:0,1)NH4ClGoodGoodGood>2 months
I-16Resin 2+ phenol-formaldehyde resin (1:0,1)NH4NO3GoodGoodGood>2 months
I-17Smo is a 2+ phenol-formaldehyde resin (1:0,1) Maleic acidSoftening (however appearance good)---
I-18Resin 2+ polytetrahydrofuran (1:0,1)NH4ClGoodGoodGood>2 months
I-19Resin 2+ polytetrahydrofuran (1:0,08)NH4NO3GoodGoodGood>2 months
I-20Resin 2 +3-aminopropyltriethoxysilane + polytetrahydrofuran (1:0,1:0,1)NH4ClGoodGoodGood>2 months
I-21Resin 2 +3-aminopropyltriethoxysilane + polytetrahydrofuran (1:0,1:0,1)NH4NO3GoodGoodGood >2 months

Table 2
The results of the mechanical tests
Number exampleResinThe hardenerFlexural strength σm[MPa]Stress at rupture σr[MPa]
II-1Resin 1Maleic acid3,13,09
II-2Resin 2NH4Cl3,72to 1.86
II-3Resin 2NH4NO33,431,71
II-4Resin 2Maleic acid1,020
II-5Resin 3NH4Cl4,192,09
II-6 Resin 3NH4NO34,722,35
II-7Resin 3Maleic acid1,430
II-8Resin 2+ phenol-formaldehyde resin (1:0,1)NH4Cl5,482,74
II-9Resin 2+ phenol-formaldehyde resin (1:0,1)Maleic acid1,180
II-10Resin 2+ polytetrahydrofuran (1:0,1)NH4Cl3,93is 3.08
II-11Resin 2+ polytetrahydrofuran (1:0,08)NH4NO33,14of 1.57
II-12Resin 2+ polytetrahydrofuran (1:0,08)Maleic acid0,530
II-13Smo is a 2+ 3-aminopropyltrimethoxysilane (1:0,05) NH4Cl3,211,6
II-14Resin 2+ 3-aminopropyltrimethoxysilane (1:0,05)NH4NO34,172,08
II-15Resin 2+ 3-aminopropyltrimethoxysilane (1:0,05)Maleic acid0,640
II-16Resin 2+ 3-aminopropyltriethoxysilane (1:0,11)NH4Cl3,751,88
II-17Resin 2+ 3-aminopropyltrimethoxysilane (1:0,11)Maleic acid1,50
II-18Resin 2+ 3-aminopropyltrimethoxysilane + formaldehyde resinNH4Clthe 3.651,83
II-19Resin 2+ 3-aminopropyltrimethoxysilane + formaldehyde resinNH4NO3 3,191,59
II-20Resin 2+3-aminopropyltrimethoxysilane + formaldehyde resinMaleic acid3,541,77
II-21Resin 2+ 3-aminopropyltriethoxysilane + polytetrahydrofuran (1:0,1:0,1)NH4Cl0,420
II-22Resin 2+ 3-aminopropyltriethoxysilane + polytetrahydrofuran (1:0,1:0,1)NH4NO31,140
II-23Resin 2+ 3-aminopropyltriethoxysilane + polytetrahydrofuran (1:0,1:0,1)Maleic acid0,670
II-24Resin 2+ glycolNH4NO30,140

Number exampleResinThe hardenerFirmly the th Flexural σ m[MPa]Stress at rupture σr[MPa]
II-25Resin 2+ glycolMaleic acid0,740
II-26Resin 3+ 3-aminopropyltriethoxysilane (1:0,13)NH4ClToo soft sampleToo soft sample
II-27Resin 3+ 3-aminopropyltriethoxysilane (1:0,13)Maleic acid1,160
II-28Resin 4NH4ClThe destruction of the sample before test
II-29Resin 4Maleic acid2,270
II-30Resin 4+ 3-aminopropyltrimethoxysilaneNH4Cl0,910
II-31Resin 4+ 3-aminopropyl trimethoxysilane Maleic acid3,121,55
II-32Resin 4+ 3-aminopropyltriethoxysilaneNH4NO30,460
II-33Resin 4+ 3-aminopropyltriethoxysilaneMaleic acid2,431,21
II-34Resin 4+ glycolNH4Cl2,631,32
II-35resin 4+ glycolMaleic acid3,431,71

The second series of experiments

To perform the second series of experiments synthesize the following urea-formaldehyde resin.

Resin 5 Esterified with n-butanol urea-formaldehyde resin based on urea (1 mol), formaldehyde (1.8 mol), n-butanol (0.6 mol) and 1,4-butanediol (0.5 mol) in solution in n-butanol with a resin content of about 60% of the mass.

Resin 6 Esterified with methanol urea-formaldehyde smolana the basis of urea (1 mol), formaldehyde (2.3 mol), methanol (0.6 mol) and 1,4-butanediol (0.5 mol) (resin contains no solvent).

Resin 7 Esterified with methanol urea-formaldehyde resin based on urea (1 mol), formaldehyde (2.2 mol), methanol (1.0 mol) and 1,4-butanediol (0.5 mol) in solution in water with a resin content of about 75% of the mass.

Resin 8 Esterified with n-butanol urea-formaldehyde resin based on urea (1 mol), formaldehyde (2.3 mol) and n-butanol (1.3 mol) in solution in n-butanol with a resin content of about 85% of the mass.

The preparation used for testing samples

For preparation of samples of 5 g of each of resins at room temperature and mixed with 1 g of an aqueous solution of hardener (35% of the mass. hardener in water). In the case of the two hardeners their ratio is 1:1. Then add sand with approximate particle sizes from 0.3 to 0.8 mm, and the components are mixed. From the mixture obtained in silicone form is made samples in the form of rods of length 8 cm, width 1 cm and thickness 0.4 cm, which utverjdayut for one hour at 140°C. the Cured samples extracted from the form. Properties of the samples are given in table 3.

In another series of experiments the curing of the samples performed at room temperature.

Sample preparation using the modified resins

<> 10 g of the resin 5, 6 or 7 is mixed with 2 g of an aqueous solution of the curing agent (maleic anhydride + ammonium nitrate in a ratio of 1:1, 35% of the mass. in water) and 1 g of the additive concerned. Immediately after this, add 100 g of sand with an approximate particle size of from 0.3 to 0.8 mm, and the components are mixed. In the case of use as an additive silanes is not injected into the resin and mix directly with sand, which is then dried for 10 minutes. Molded samples in the form of bars which utverjdayut for 1 hour at 140°C.

Varying the concentration of the resin

The required amount of resin 7 is mixed with 20% of the mass. solution of the corresponding hardener (35% of the mass. in p-toluensulfonate). Immediately after this, add 50 g of sand and molded samples in the form of bars which utverjdayut for one hour at 140°C.

Vary the ratio of sand to the resin. Mechanical properties of the samples are shown in table 11.

Tests in terms of technical application

The oil resistance

Half of the corresponding sample (length 4 cm, width 1 cm, thickness 0.4 cm) incubated at room temperature in oil. Daily by gently turning the sample by using a rod to check if he kept stable or partially or completely destroyed. The results are appropriate to estoodeeva tests are shown in table 3.

Water resistance

Half of the corresponding sample (length 4 cm, width 1 cm, thickness 0.4 cm) incubated at room temperature in 100 ml of water. Daily performed by using a rod careful rolling sample check if he kept stable or partially or completely destroyed. The results of the respective tests are shown in table 4.

Resistance to salt solutions

Tests perform similarly to the above testing resistance, however, as the environment of the use of saline solution (89,4 g NaCl, 52,94 g CaCl·2H2O, to 15.06 g MgCl2·6H2O in 1 liter of distilled water). The results of tests of samples solidified at 140°C, are shown in table 5, the samples solidified at room temperature, in table 7.

Flexural strength

Sample strength Flexural determine, as described above, according to DIN EN ISO 178. The results of tests of samples solidified at 140°C, are shown in table 6, the samples solidified at room temperature, in table 8; the dependence of the tensile strength in bending from the resin concentration is given in table 11.

The temperature of destruction

The temperature of degradation of the individual samples is determined by the method of differential scanning calorimetry (DSC). The results of the respective measurements are shown in table 9.

Results the ATA test containing modified resin samples for suitability for technical applications are given in table 10.

Table 3
Curing at 140°C, the oil resistance, the components of the curing agent in the ratio of 1:1
The hardenerResin 5Resin 6Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)The esterification of butanol (resin obtained without diol)
Maleic anhydride/ammonium nitrate>3 months>3 months>3 months*
Maleic anhydride/ammonium sulfate>3 months>3 months>3 monthsfrom 1 to 4 days
Maleic anhydride/ammonium phosphate>3 months> months >3 monthsfrom 1 to 4 days
Maleic anhydride/ammonium bromidefrom 11 to 12 days>3 months>3 months*
p-toluensulfonate>3 months>3 months>3 months*
Methansulfonate/ammonium nitrate<1 day>3 months>3 months*
Methansulfonate/ammonium sulfate<1 day>3 months>3 months*
Methansulfonate/ammonium phosphate<1 day>3 months>3 months*
Methansulfonate/ammonium bromide<1 dayfrom 5 to 6 days>3 monthsfrom 1 to 4 days
Formic acid/ammonium nitrate>3 months>3 months>3 months*
Formic acid/ammonium sulfate>3 months>3 months>3 months<1 day
Formic acid/ammonium phosphate>3 months>3 months>3 months>3 months
Formic acid/ammonium bromide>3 months>3 months>3 months*
Phosphoric acid/ammonium nitrate>3 months>3 months>3 months*
* The sample is destroyed already when removing from the silicone mold, and therefore the definition of resistance is not possible

Table 4
Curing at 140°C, the resistance components of the hardener in the ratio of 1:1
The hardenerResin 5Resin 6Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)The esterification of butanol (resin obtained without diol)
Maleic anhydride/ammonium nitrate>3 months>3 months>3 months*
Maleic anhydride/ammonium sulfate>3 months>3 months>3 monthsfrom 2 to 3 days
Maleic anhydride/ammonium phosphate>3 monthsfrom 8 to 9 daysfrom 8 to 9 daysfrom 3 to 6 days
Maleic anhydride/b is Omid ammonium >3 months>3 months>3 months*
p-toluensulfonate>3 months>3 months>3 months*
Methansulfonate/ammonium nitrate>3 months>3 months>3 months*
Methansulfonate/ammonium sulfate>3 months>3 monthsfrom 10 to 13 days*
Methansulfonate/ammonium phosphatefrom 10 to 13 daysfrom 8 to 9 daysfrom 8 to 9 days*
Methansulfonate/ammonium bromide>3 monthsfrom 8 to 9 daysfrom 10 to 13 daysfrom 2 to 3 days
Formic acid/ammonium nitrate>3 months>3 month is in >3 months*
Formic acid/ammonium sulfate>3 months>3 monthsfrom 10 to 13 daysfrom 3 to 6 days
Formic acid/ammonium phosphate>3 monthsfrom 8 to 9 days>3 months>3 months
Formic acid/ammonium bromide>3 months>3 months>3 months*
Phosphoric acid/ammonium nitrate>3 months>3 months>3 months*
* The sample is destroyed already when removing from the silicone mold, and therefore the determination of the water resistance is not possible

Table 5
Curing at 140°C, resistance to salt solutions, the components of the CTE is the leader in the ratio of 1:1
The hardenerResin 5Resin 6Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)The esterification of butanol (resin obtained without diol)
Maleic anhydride/ammonium nitrate>3 months>3 months>3 months*
Maleic anhydride/ammonium sulfate>3 monthsfrom 8 to 11 days>3 months<1 day
Maleic anhydride/ammonium phosphate>3 months>3 monthsfrom 5 to 6 daysfrom 1 to 4 days
Maleic anhydride/ammonium bromide>3 months>3 months is s >3 months*
p-toluensulfonate>3 months>3 months>3 months*
Methansulfonate/ammonium nitrate>3 months>3 months>3 months*
Methansulfonate/ammonium sulfate>3 monthsfrom 8 to 11 days>3 months*
Methansulfonate/ammonium phosphatefrom 8 to 11 daysfrom 6 to 7 daysfrom 6 to 7 days*
Methansulfonate/ammonium bromidefrom 8 to 11 days>3 months>3 months<1 day
Formic acid/ammonium nitrate>3 months>3 months>3 months*
Formic acid/ammonium sulfate>3 months>3 monthsfrom 11 to 12 daysfrom 1 to 4 days
Formic acid/ammonium phosphate>3 months>3 monthsfrom 4 to 5 days<1 day
Formic acid/ammonium bromide>3 months>3 months>3 months*
Phosphoric acid/ammonium nitrate>3 months>3 months>3 months*
* The sample is destroyed already when removing from the silicone mold, and therefore the determination of its resistance to salt solutions is not possible

Table 6
Curing at 140°C Flexural strength σm[MPa], the components of the curing agent in the ratio of 1:1
The hardener Resin 5Resin 6Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)The esterification of butanol (resin obtained without diol)
Maleic anhydride/ammonium nitrate1,809,059,62*
Maleic anhydride/ammonium sulfate4,74to 6.197,371,38
Maleic anhydride/ammonium phosphate5,617,53of 5.924,15
Maleic anhydride/ammonium bromide2,879,365,97*
p-toluensulfonate6,568,18 9,96*
Methansulfonate/ammonium nitrate0,89to 6.806,46*
Methansulfonate/ammonium sulfate0,34to 4.683,98*
Methansulfonate/ammonium phosphate0,70to 3.586,36*
Methansulfonate/ammonium bromide0,194,393,760,56
Formic acid/ammonium nitrate3,329,047,60*
Formic acid/ammonium sulfatethe 5.256,79to 7.321,77
Formic acid/ammonium phosphate3,925,073,662,81
Formic acid/ammonium bromide4,107,139,50*
Phosphoric acid/ammonium nitrate1,597,54of 6.71*
* The sample is destroyed already when removing from the silicone mold, and therefore the testing is not possible;
values above 7 MPa are the best

The esterification of butanol (resin obtained without diol)
Table 7
Curing at room temperature, resistant to salt solutions, components hardener in the ratio of 1:1
The hardenerResin 5Resin 6Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)
Maleic anhydride/ammonium nitrate>3 months>3 months>3 monthsfrom 9 to 10 days
Maleic anhydride/ammonium sulfate>3 months>3 months>3 months>3 months
Maleic anhydride/ammonium phosphate>3 months>3 monthsfrom 5 to 6 days>3 months
Maleic anhydride/ammonium bromide>3 months>3 months>3 monthsfrom 9 to 10 days
p-toluensulfonate>3 months>3 months>3 months>3 months
Methansulfonate/ammonium nitrate>3 months>3 months>3 months from 7 to 8 days
Methansulfonate/ammonium sulfate>3 months>3 months>3 months>3 months
Methansulfonate/ammonium phosphate>3 months>3 months>3 months>3 months
Methansulfonate/ammonium bromide>3 months>3 months>3 months>3 months
Formic acid/ammonium nitrate>3 months>3 months>3 months>3 months
Formic acid/ammonium sulfate*>3 months>3 months>3 months
Formic acid/ammonium phosphate***
Formic acid/br the MFA ammonium >3 months>3 months>3 months>3 months
Phosphoric acid/ammonium nitrate>3 months>3 months>3 months>3 months
* The sample is destroyed already when removing from the silicone mold, and therefore the determination of its resistance to salt solutions is not possible

Table 8
Curing at room temperature, Flexural strength σm[mpa], the components of the curing agent in the ratio of 1:1
The hardenerResin 5Resin 6Resin 7
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)
Maleic anhydride/NIT is at ammonium -5,515,71
Maleic anhydride/ammonium sulfate--2,89
Maleic anhydride/ammonium phosphate-1,131,13
Maleic anhydride/ammonium bromide-6,126,83
p-toluensulfonate5,56at 9.538,83
Methansulfonate/ammonium nitrate3,756,47to 7.77
Methansulfonate/ammonium sulfate2,477,027,07
Methansulfonate/ammonium phosphate1,81of 6.785,44
Methansulfonate/ammonium bromide4,678,238,56
Formic acid/ammonium nitrate-7,09-
Formic acid/ammonium sulfate---
Formic acid/ammonium phosphate---
Formic acid/ammonium bromide-8,73-
[phosphoric acid/ammonium nitrate---
* The sample is destroyed already when removing from the silicone mold, and therefore the testing is not possible;
values above 7 MPa are the best

Resin 6
Table 9
Temperature destruction of samples with sand, respectively comparative samples without sand, measured using DSC
The hardenerResin 5Resin 7Resin 8
The esterification of butanol (resin obtained by using a diol)Etherification with methanol (resin obtained by using a diol)Etherification with methanol (solution of the resin in water)The esterification of butanol (resin obtained without diol)
Maleic anhydride/ammonium nitrate, drying at 140°C274°C268°C263°C232°C
Maleic anhydride/ammonium nitrate, curing at room temperature268°C281°C271°C230°C
Ammonium nitrate, drying at 140°C, the resin without sand266°C280°C273°C210°C

Table 10
The test results of the modified resins in terms of technical p is imeneniya
AdditiveThe oil resistance
Resin 5Resin 6Resin 7
BDO<1 day>3 months>3 months
Polytetrahydrofuran>3 months>3 months>3 months
Glycerin<1 day>3 months>3 months
Diethylene glycol<1 day>3 months>3 months
3-Aminopropyltriethoxysilane>3 months>3 months>3 months
3-Aminopropyltrimethoxysilane>3 months>3 months>3 months
AdditiveThe resistance of the salt solutions
Resin 5Resin 6Resin 7
BDO<1 day>3 months>3 months
Polytetrahydrofuran>3 months>3 months>3 months
Glycerin<1 day>3 months<1 day
Diethylene glycol<1 day>3 months<1 day
3-Aminopropyltriethoxysilane>3 months>3 months>3 months
3-Aminopropyltrimethoxysilane>3 months>3 months>3 months
AdditiveWater resistance
Resin 5Resin 6Resin 7
BDO<1 day>3 months<1 day
Polytetrahydrofuran<1 day>3 months>3 months
Glycerin<1 day>3 months<1 day
Diethylene glycol<1 day>3 months<1 day
3-Aminopropyltriethoxysilane>3 months>3 months>3 months
3-Aminopropyltrimethoxysilane>3 months>3 months>3 months
AdditiveFlexural strength [MPa]
Resin 5Resin 6Resin 7
BDO0,314,43 1,66
Polytetrahydrofuran1,4813,889,82
Glycerin0,103,450,69
Diethylene glycol0,283,701,70
3-Aminopropyltriethoxysilane5,5614,6712,09
3-Aminopropyltrimethoxysilane6,1212,9414,64

Table 11
Sample strength in bending, depending on the amount of resin used (paired values correspond to the results of a double-strength determination made in order to get an idea about the measurement error)
The amount of resin 7 (based on sand)Flexural strength [MPa]
3% of the mass.7,2/8,6
7% of the mass. 14,3/12,8
10% of the mass.16,5
15% of the mass.27,6
25% of the mass.29,2/27,8

The above examples show that in all the test samples based resins 5, 6 and 7, containing structural units of the formula (II), to achieve the best results in comparison with samples based resin 8, not containing these structural units. Samples of the resin 8 in many cases it is impossible to extract from the mold without damage, while they, as a rule, have lower resistance to water, oil and salt solutions. In addition, sample-based resins 5, 6 and 7 have a higher thermal stability.

Sample strength in bending as increase the amount of resin relative to the amount of sand increases, however, since the amount of resin 15 wt. -%, increase the strength of the samples is almost terminated.

1. A method of binding a non-monolithic inorganic oxide material selected from the group including:
- material containing particles of inorganic oxide materials, and
- oxide inorganic materials which have pores, cracks, fractures or fissures,
through the implementation of the contact n of the organic material with the curable composition, containing at least one curable esterified aminoplasmal, and subsequent thermal curing resin, wherein the esterified by aminoplasmal is etherified urea-formaldehyde resin containing the structural units of the General formula (I) and/or (II):


in which
R1, R2, R3 and R4 denote substituents selected from the group comprising H, -CH2-OH and-CH2-OR',
R' represents an aliphatic hydrocarbon residue with 1-10 carbon atoms,
X denotes a number from 2 to 8 and
Y represents a number from 1 to 20,
provided that at least one of the residues R1, R2, R3 and R4 denotes-CH2-OR',
moreover, the amount of curable composition is from 0.5 to 60 wt.% in terms of inorganic materials and the curing is carried out at a temperature of from more than 0 to 280°C.

2. The method according to claim 1, characterized in that compounds of the formula (II) is obtained by an additional interaction of the compounds of formula (I) with diatomic alcohol of General formula (III):

in which X and Y are specified in claim 1 values.

3. The method according to claim 1, wherein the curable composition further comprises at least one solvent.

4. The method according to claim 3, characterized in that the solvent is the fast water or mixtures of water with alcohol.

5. The method according to claim 1, wherein the curable composition further comprises at least one acid compound.

6. The method according to claim 1, characterized in that under a non-monolithic oxide inorganic materials include silica and/or silicate minerals.

7. The method according to claim 1, characterized in that under a non-monolithic inorganic oxide materials mean inorganic oxide particles.

8. The method according to claim 7, characterized in that the size of the inorganic oxide particles is from 0.01 to 2 mm.

9. The method according to claim 7 or 8, characterized in that the inorganic oxide particles are mixed with the curable composition, and the resulting mixture was formed into a molded product, which utverjdayut.

10. The solid composition of the inorganic oxide particles and utverzhdenii resin, manufactured by the method according to one of claims 1 to 8.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: disclosed is complex of ceramic particles, which contains multitude of separate loose particles, which can be applied in a range different industrial processes and products, including, for instance, abrasive media as granular coating of roofing shingles based on bitumen, as filtering medium for liquids, as sand substituent in processes of casting on melted models and as propants in drilling works with DTH hammer, in which ceramic particles can be named propants. This multitude has complete weight and granulometric composition of particles. Effective width of granulometric composition exceeds 100 microns and contains three adjoining and non-crossing areas, which include first area, second area and third area. First area adjoins second area, and second area adjoins third area. Width of second area constitutes, at least, 25% of effective width. Weight of particles in second area does not exceed 15% of complete weight of multitude of particles. Weight of particles in first area and third area each exceeds weight of particles in second area.

EFFECT: complex of particles, possessing certain characteristics for increasing resistance to crushing, specific conductivity and stability to sedimentation with simultaneous reduction of production costs for enterprise producing ceramic particles.

24 cl, 2 tbl, 4 dwg, 1 ex

FIELD: oil and gas industry.

SUBSTANCE: water-based drilling mud is suggested with the following composition, in kg/m3: aggregating agent Base Medium B 10-40; KOH 0.05-0.3; rheology regulator component Poliksan 1.5-4.0; mud filtration regulator component Osnopak NO 0.8-3.0; rheology and filtration regulator component Osnopak VO 0.5-1.0; filtration regulator component Amilor R-122 12-30; pH regulator, swelling inhibitor - hydrated lime 2-5; swelling inhibitor - gypsum 15-18; potassium alum AlgypoDS-103 1,0-3,0; colmatant-filler UMS-100 40-200; process water - remaining volume up to 1 cubic metre, and the method for drill mud production.

EFFECT: ensuring high inhibiting and low dispersing properties of the drill mud, low water loss preventing slides and collapses, reducing moisturising properties of the mud.

2 cl, 2 tbl

FIELD: oil and gas industry.

SUBSTANCE: in the method of ceramic proppants producing that includes grinding of source charge mixture, formation of granules and their baking the latter is performed in two stages - at the first stage preliminary baking of raw proppant granules takes place at a temperature of 700-950°C, thereafter baked granules are treated by saturated water solution of inorganic salt of lithium, potassium or sodium or their mixture and at the second stage final baking of granules takes place in order to reach the maximum strength of the granules. Invention has been developed in dependent claims.

EFFECT: improving solubility in acids while using acid treatment.

4 cl, 2 dwg, 5 ex, 5 tbl

FIELD: oil and gas industry.

SUBSTANCE: process fluid for perforating and killing of oil wells contains wt %: surface-active substance of combined effect SNPH PKD-515 - 0.5; potassium formate - 10-50; process or sea water - 49.5-89.5.

EFFECT: increasing density of the process fluid, reducing the number of its components, extending its range of use.

1 ex, 2 dwg, 1 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention refers to oil and gas field, namely to methods for preparing materials applied for oil and gas well casing. The method for preparing disperse fibre-reinforced backfill containing a mineral binder, mixing water and fibrous modifying agent coiled and mixed with the mineral binder in dry form includes mixing of the dry mix of the binder and fibrous modifying agent with water; portland cement is used as a binder, each fibre of the modifying agent has a dumbbell thickening at the ends or additional fibres with length of 1/3 of the main fibre are connected to the main fibre ends at the angle of 30-90°.

EFFECT: improving adhesion degree of fibres with cement matrix thus allowing use of advantage of disperse fibre-reinforced composites.

1 dwg, 5 ex

FIELD: oil and gas industry.

SUBSTANCE: invention refers to oil and gas industry, and namely to the manufacturing procedure of ceramic proppants intended to be used as propping agents at production of oil or gas using hydraulic fracturing method. The manufacturing procedure of magnesian-quartz proppants includes treatment of the stock, wet milling, granulating and annealing of granules. Wet milling is made in a ball crusher charged with a mix of metal grinding bodies and grinding bodies made of the stock used for production of magnesian-quartz proppants with the following ratio of charged components, wt %: metal grinding bodies 37-55, mill feed 26-30, magnesian-quartz grinding bodies 37-15, at that coefficient of the crusher charge is equal to 0.48-0.55.

EFFECT: reducing breakability of proppant granules due to improved quality of the stock milling.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to water-based gelling liquids for processing underground formations. Composition for reducing time of linking of water solutions of linked organic polymer includes said polymer, mixed with aqueous basic liquid, borate linking agent, which has solubility in water at 22°C (71.6°F) in the range from 0.01 kg/m3 to 10 kg/m3, and composition of linking modifier in amount, reducing time of linking, which increases rate, at which linking agent provides gelling of linked organic polymer, where composition of modifier contains 90-98% vol. of the first and 2-10% vol. of the second modifiers of linking. Method of underground formation processing includes obtaining liquid for processing, which includes mixing aqueous basic liquid and linked thickening organic polymer, soluble in aqueous basic liquid, hydration of liquid for processing, obtaining borate-based linking composition, which contains borate linking agent, which has solubility, mentioned above; obtaining solution of modifier of linking, which contains 90-98% vol. of the first and 2-10% vol. of the second modifiers of linking; mixing linking composition and solution of modifier of linking; addition of obtained mixed composition to hydrated liquid and delivery of liquid for processing into underground formation. Invention is developed in dependent claims.

EFFECT: increased efficiency of control of linking in case of changing pH and in wide interval of temperatures in formation.

21 cl, 10 ex, 13 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention is related to oil well drilling. The method for provision of substantially permanent mud flow characteristics within the temperature range from about 120°F (49°C) up to about 40°F (4°C) includes addition to drilling mud of an additive that contains the product of carboxylic acid reaction having at least two carboxyl fragments and polyamine with at least two functional amine groups provided that the additive does not contain alkoxylated alkylamides and/or amides of fatty acids. The composition consists of the product of carboxylic acid reaction having at least two carboxyl fragments and polyamine with at least two functional amine groups provided that the additive does not contain alkoxylated alkylamides and/or amides of fatty acids. The oil-based drilling mud contains the above composition.

EFFECT: improving efficiency of rheology regulation within the wide temperature range for horizontal drilling and deep water areas.

47 cl, 4 ex, 5 tbl

FIELD: oil and gas industry.

SUBSTANCE: method includes grinding of preliminary treated feed stock based on natural silica and feldspar sand and serpentine rock, its granulating and sintering; during grinding low-melting red-burning clay is added additionally to the feed stock with the following ratio of components, % by weight: silica and feldspar sand - 70-90, serpentine rock - 5-15, red-burning clay - 5-15, at that the clay is dried preliminary at temperature of 200-400°C and sintering of granules is made at temperature of 1100-1200°C. The invention is well-developed in the subclaim.

EFFECT: increased strength of proppant.

2 cl, 2 ex, 2 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention relates to consolidation of liquid stages and can be applied to fluid system used for injection into a well. Method for consolidation maintenance of liquid stages in the fluid system used for injection into a well containing an interfacial fluid of another origin adjoining to the liquid stage lies in mixing of solid particles to at least liquid stage or to adjoining interfacial fluid in quantity when discrete borders of the interfacial fluid are formed between the stage and adjoining interfacial fluid and further injection of fluid system into the well bore. Method for consolidation maintenance of liquid stages in the fluid system used for injection into the well containing an interfacial fluid of another origin adjoining to the liquid stage lies in mixing of solid particles to at least liquid stage or to adjoining interfacial fluid in quantity when in streamline conditions discrete borders of the interfacial fluid are formed between the stage and adjoining interfacial fluid and at least a part of solid particles have adhesion properties promoting aggregation of solid particles at least inside the liquid stage or adjoining interfacial fluid and further injection of fluid system into the well bore.

EFFECT: ensuring successful hydraulic fracturing.

42 cl, 3 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: composite material contains drilling wastes, portland cement in amount of 5-10% of the volume of the drilling wastes, technical carbon 0.5-1% of the volume of drilling wastes, quick lime 3-5% of the volume of drilling wastes, peat 20-40% of the volume of drilling wastes, sand 10-30% of the volume of the drilling wastes, phosphorus-containing mineral fertiliser 20-30 kg per ton of the composite material. The phosphorus-containing mineral fertiliser can be diammonium phosphate, ammonium nitrate phosphate fertiliser, ammophos with potassium sulphate or potassium chloride in ratio of 70:30 wt %, diammophos with potassium sulphate or potassium chloride in ratio of 70:30 wt %. The composite material further contains hydrocarbon-based spent or unused drilling fluid with hydrocarbon content of 3-5% of the volume of the drilling wastes.

EFFECT: use of the present composite material provides effective recultivation of disturbed soils while recycling hazardous drilling wastes and improves the environment.

8 cl, 3 ex

FIELD: construction.

SUBSTANCE: method consists in treatment of the latter by a stabiliser containing latex polymer, which is applied mixed with water. Treatment of soil or foundation is carried out by introduction of the stabiliser by means of a cutter by the cutting method as the stabiliser is mixed with ground or foundation. The latex polymer is represented by latexes from the group that includes sterol-butadiene latex, (meth)acrylate latex, ethylene-vinyl acetate latex, ethylene/propylene latex, ethylene/propylene-dimer latex, butadiene-acrylonitrile latex, silicon latex, polybutadiene latex, latex from natural rubber or mixture of two or several of the specified latexes. The stabiliser additionally comprises a thickener based on cellulose, a defoaming agent selected from the group including silicons, glycol ethers, natural fats or oils and fatty alcohols, and also at least one chloride or at least one hydroxide of alkaline or earth metal, besides, the stabiliser has the following composition (wt %); 0.1 - 50 latex polymer, 0.05 - 5 thickener, up to 5 defoaming agent, 0.01 - 10 chloride or hydroxide of alkaline or earth metal, residue to 100 - water.

EFFECT: fixation and stabilisation of soils or foundations, making it possible without removal and recycling of oil soil and special costs to perform construction-earth works.

6 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: three types of clay of different chemical composition is used with addition of molasses and Linex biopreparation in the following ratios, wt %: Dialbeculit clay -38-40; Irlit clay 1 - 28-32; Irlit clay 7 - 16-20; molasses - 8-12; Linex biopreparation -2-4. Adding such a composition to the soil reduces the amount of oil pollutants by 72%.

EFFECT: low toxicity of soil and expenses on amelioration.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to soil and ground chemical propping compositions and can be used in agriculture against water and wind erosion, as well as in construction of roads and other earth structures. The disclosed aqueous soil and ground propping composition contains 0.90-4.62 wt % of a charged polyelectrolyte complex and 0.08-0.87 wt % of a salt of an alkali metal or ammonia. The charged polyelectrolyte complex in said composition is a product of reacting water-containing solutions of a cationic polyelectrolyte, which contains chloride and bromide counter-ions, and an anionic polyelectrolyte from a group which includes a sodium salt of carboxymethyl cellulose, an alkali metal or ammonium salt of a polyacrylic acid or polymethacrylic acid, taken in a ratio where content of charged links of one polyelectrolyte ranges from 51% to 60% of the content of charged links of the other polyelectrolyte.

EFFECT: compared to the closest counterpart, the disclosed composition provides efficient soil and ground propping from wind erosion while reducing content of salt in the composition from 1,5-3,7 wt % to 0,08-0,87 wt % and consumption of the composition from 1-2 l/m2 to 0,3-0,45 l/m2.

9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to soil and ground chemical propping methods and can be used in agriculture against water and wind erosion, as well as in construction of roads and other earth structures. The method involves mixing aqueous solutions of an anionic polyelectrolyte and a cationic polyelectrolyte and a water-soluble salt. The polyelectrolytes are mixed with their total initial concentration ranging from 1 to 10 wt % in a ratio at which content of charged links of one polyelectrolyte is equal to 5-50% of the content of charged links of the other polyelectrolyte and concentration of at least one salt, selected from a group comprising an alkali metal salt, an ammonium salt, a calcium salt and a magnesium salt, ranges from 0.01 to 0.1 wt %.

EFFECT: low content of salt in the composition and lower consumption rate of the composition.

7 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to soil and ground chemical propping compositions and can be used in agriculture against water and wind erosion, as well as in construction of roads and other earth structures. The composition contains a polyelectrolyte, a water-soluble salt and water. The polyelectrolyte is a charged polyelectrolyte which is a reaction product of aqueous solutions of a cationic polyelectrolyte and an anionic polyelectrolyte, selected from a group comprising a sodium salt of carboxymethyl cellulose, an alkali metal or ammonium salt of polyacrylic acid or polymethacrylic acid, taken in a ratio at which content of charged links of one polyelectrolyte is equal to 5-50% of the content of charged links of the other polyelectrolyte, and the salt is an alkali metal or ammonium salt, or a mixture of such a salt with a calcium or magnesium salt, with the following ratio of components, wt %: reaction product 0.91-9.91; water-soluble salt of aqueous solutions of the cationic and anionic polyelectrolytes 0.10-0.62; water - the balance.

EFFECT: low content of salt in the composition and lower consumption rate of the composition.

9 ex

FIELD: agriculture.

SUBSTANCE: invention relates to the field of recultivation of damaged soil in conditions of the Far North and may be used when restoring the soil and vegetation layer disturbed by industrial and economic human activities. The method of recultivation of damaged soil is described, including introduction into the ground of bentonite clay, seeds of perennial grasses, fertilisers, humic compounds and binder, and the bentonite clay is inserted as part of the waste mud, followed by stirring the top layer of soil. Then the fertiliser, humic compounds and seeds of perennial grasses are inserted, and then a binder is inserted, which is used as a solution of xanthan gum.

EFFECT: invention provides a more efficient process of recultivation, expansion of the scope of application on the surface of soils with different steepness.

2 ex

FIELD: agriculture.

SUBSTANCE: sapropel and natural loosener are ploughed into soil at the depth of 10-15 cm. Natural loosener is represented by siftings of open pits of construction materials, at the following weight ratio of components, %: sapropel 8-12%; siftings of pits of construction materials 13-32%; upper layer of clayey soil - balance.

EFFECT: increased bioproductivity of soils and protection of recultivated soils against wind erosion.

1 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture and may be used to reduce soil acidity, improve its structure and fertility. Method implies soil application of deoxidiser, which is a mixture of organic and mineral components with a deoxidising agent. Peat of 30-70% decay degree and pH 3.5-4.5 is used as organic component, borogypsum is used as mineral component and 53% alkaline solution (potassium hydroxide) is used as deoxidising agent. Ratio of components (kg per 1 tonn of resulting deoxidiser) is as follows: peat of 30-70% decay degree and pH 3.5-4.5 1200-1230, 53% potassium hydroxide solution 48-49, borogypsum 70-74. Deoxidising agent is applied in amount of 2-3 t per 1 ha.

EFFECT: reduced soil acidity, improved structure and fertility.

4 tbl

FIELD: chemistry.

SUBSTANCE: binding composition for processing material of solid particles with formation of solid aggregated matrix is prepared including the following stages: blending of polar solvent and additional quantity of urea; addition of emulsified bitumen; addition of ureaformaldehyde precondensate; addition of other binding promotors in order to enhance bonding between the binding composition and solid particles; addition of sugar into weak organic acid; addition of weak organic acid mixed with sugar with formation of the binding composition; blending of binding composition with solid particles, which harden during over 30 minutes while mixing with above mentioned material of solid particles, besides weak organic acid is being chosen to ensure pH value of binding composition from 2.0 to 5.3.

EFFECT: binding composition was prepared for processing of materials of solid particles.

51 cl, 15 dwg, 3 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: binding composition for processing material of solid particles with formation of solid aggregated matrix is prepared including the following stages: blending of polar solvent and additional quantity of urea; addition of emulsified bitumen; addition of ureaformaldehyde precondensate; addition of other binding promotors in order to enhance bonding between the binding composition and solid particles; addition of sugar into weak organic acid; addition of weak organic acid mixed with sugar with formation of the binding composition; blending of binding composition with solid particles, which harden during over 30 minutes while mixing with above mentioned material of solid particles, besides weak organic acid is being chosen to ensure pH value of binding composition from 2.0 to 5.3.

EFFECT: binding composition was prepared for processing of materials of solid particles.

51 cl, 15 dwg, 3 tbl, 11 ex

Up!