RU2213844C1 - Method of grouting mortar-preparation - Google Patents

Abstract

FIELD: methods of preparation of grouting mortars applicable in well cementing in oil and gas producing industry. SUBSTANCE: method includes dissolving in water of modifying reagent and superplasticizer S-3 based on sodium salt of product of condensation of naphthalenesulfonic acid and formaldehyde with subsequent mixing with oil-well Portland cement. Grouting mortar is prepared with 0.30-0.35 water-cement ratio. Modifying reagent is used in form of still bottoms of monoethanolamine - waste of cleaning of process gases with monoethanolamine in ammonia production. Still bottoms in amount of 0.1-0.3% of cement weight are dissolved in 90-92% of water of its total amount and mixed with oil-well Portland cement and subsequent mixing of forming suspension for 10-15 min, and superplasticizer 5-3 in amount of 0.7-1.5% of cement total weight is dissolved in remained water and mixed with suspension. EFFECT: higher quality of well lining due to use of grouting mortar with improved main mechanical and physical properties whose setting results in formation of strong cement stone with low permeability and higher adhesion to metal. 3 tbl, 12 ex

Description

 The invention relates to methods for the preparation of cement slurries (TR), intended for cementing wells in the oil and gas industry.

 Analysis of the current level of technology showed the following.

 A known method of preparation of TP with a water-cement ratio (W / C) of 0.35-0.45 by dissolving in water the superplasticizer C-3 based on the sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde in an amount of 0.3-1.5% by weight of cement with subsequent mixing with grouting Portland cement (see Zeltser P.Ya., Matyushina NN Study of cement mortars with plasticizing additives. Tr. SNIIGTiMS. Improving the technology of drilling oil and gas wells in Eastern Siberia and Yakutia. Novosibirsk, 1985, p. 59 -62).

The disadvantage of this method is the low quality of the fastening of wells due to the use of TP when cementing casing strings with reduced basic physical and mechanical properties, during curing of which a non-uniform strength cement stone with high permeability and low adhesion to metal is formed. This is due to the following:
at W / C = 0.35; 0.40, with S-3 superplasticizer dissolved in water in an amount of 1.2 and 0.8% by weight of cement, mobility - TP flowability after 3 minutes (according to GOST 1581-78) of mixing corresponds to the standard value.

 Stirring for 90 minutes reduces the spreadability and corresponds to the standard value only at W / C = 0.40 and C-3 superplasticizer dissolved in water in an amount of 0.8% by weight of cement, as well as at W / C = 0.35 and C-3 superplasticizer dissolved in water in an amount of 1.6% by weight of cement.

 The cementing time of a well up to 1000 m in depth is 2-4 hours. The low flowability of the TP leads to its premature thickening in the casing when it is pushed into the annulus and, as a result, to underperformance to the required level.

 The decrease in the spreadability of TP with prolonged stirring is due to the fact that the aqueous solution of C-3 superplasticizer, when mixed with cement Portland cement, is distributed over the entire surface of the dispersed phase of TP. When mixing, cement Portland cement is dispersed with the formation of new phase interfaces, the wetting of which requires an increasing amount of water and C-3 superplasticizer, which has already been consumed and the amount of which is insufficient for plasticizing TP. As a result, there is a decrease in the plasticity of the latter. In borehole conditions, TR is in constant motion throughout the entire cementing time, and the forcing of a solution with low spreadability into the annular space leads to an increase in the selling pressure and to hydraulic fracturing, the drilling fluid is not completely displaced into the annular space, which increases the likelihood of formation of inter-fluid flows, which significantly reduces the quality of the wells.

 A known method of preparation of TR, including dissolving in water mixing retarder and accelerator setting time of cement paste and subsequent mixing of cement on it, before dissolving the reagents, the mixing water is divided into two parts, in one of which is 0.66-0.80 wt.h . dissolving the retarder of setting time, and in the other, an accelerator of setting time, and mixing the cement is carried out on the first solution, followed by mixing the resulting suspension with a second solution (see AS USSR 1460201 from 08.25.86, class E 21 B 33 / 138, publ. BI 7, 1989).

 The disadvantage of this method is the low quality of the fastening of wells due to the use of TP when cementing casing strings with insufficiently high basic physical and mechanical properties, during curing of which a weak cement stone with increased permeability and low adhesion to metal is formed. This is due to the following.

TP, prepared by a known method, has a high W / C = 0.45-0.50 and an increased amount of a retarder of setting and hardening of cement — nitrilotrimethylphosphonic acid (NTP). The dissolution of NTF in part of the water and mixing Portland cement on this solution leads to the formation of a film of insoluble calcium salt of NTF around cement particles, which is a strong inhibitor of hydration and hardening of Portland cement. When an aqueous solution of sodium liquid glass is introduced into this suspension, its orthosilicic acid very quickly reacts with calcium ions of the liquid phase of the cement suspension with the precipitation of the vitreous mass. An aqueous sodium hydroxide solution remains in the sodium liquid glass solution. He is not able to unblock cement grains from the moderator - NTF calcium salt. Therefore, in the first days, cement hydration is only partially and very slow, especially at normal hardening temperature t = 22 ^o C. The setting time of TP (beginning and end) occurs after 61-64 and 69-76 hours. As a result, TP has worsened plugging properties. Increased setting time, which significantly exceeds the estimated time of well cementing, can lead to a breakthrough of gas from the formation at the wellhead while waiting for the cement to thicken. Low sedimentation stability of this TP leads to increased water separation, which can cause channel formation in a cement stone. A cement stone after 1 day of hardening at t = 22 ^° C has not yet formed, and subsequently, due to slow hydration and hardening, the resulting stone will have increased permeability and low strength and adhesion to the metal.

 A known method of preparation of TP with W / C = 0.35-0.42 by mixing cement Portland cement with fly ash with a content of silicon dioxide of at least 30 wt.% In the ratio of wt.h. 1: 0.33-1.94, respectively, until a homogeneous free-flowing mixture is obtained, followed by mixing with the last liquid containing an aqueous solution of a plasticizer in an amount of 0.04-0.07% by weight of the free-flowing mixture and / or the setting time regulator in an amount of 4.17 - 4.26% by weight of the granular mixture (see RF patent 2136846 from 05.08.98, class E 21 B 33/138, publ. BI 25, 1999). The number of reagents used is recounted by the authors.

The disadvantage of this method is the low quality of the fastening of wells due to the use of TP when cementing casing strings with insufficiently high basic physical and mechanical properties, during curing of which a weak cement stone with increased permeability and low adhesion to metal is formed. This is due to the following:
TP, prepared by a known method, has a fairly high value of W / C = 0.35-0.42, short setting time at elevated temperatures t = 140 ^o C and long at t = 20 ^o C.

 Grouting Portland cement during the preparation of TP plays the role of an alkaline activator for fly ash during its hydration, which occurs only at elevated temperatures. Fly ash mainly contains the vitreous phase, so it does not hold gravitational water well in TR, which contributes to an increase in water separation. In addition, fly ash has a coarse dispersion, due to which the ductility of the TP deteriorates. In the case of joint use of the plasticizer - NTF and the setting time regulator, they chemically interact with the formation of the calcium salt of NTF, which reduces the plasticizing properties of such a liquid. To obtain the TP of the required spreadability, an additional flow rate of mixing liquid is required. At the same time, the permeability of cement stone increases, adhesion to the metal decreases, which does not provide reliable contact with the casing and the walls of the well. TP will also have the same disadvantages in the case of the joint use of an aqueous solution of C-3 superplasticizer and calcium chloride as a mixing liquid (see table 2). As a result of their interaction, the calcium salt of the C-3 superplasticizer oligomer is formed, which, after mixing of the cement-cement loose mixture, loses a significant part of its plasticizing ability and acquires the properties of a strong moderator of hydration and hardening. After 1 day of hardening, the formation of cement stone does not occur, which indicates the inoperability of the TP obtained by this cooking method. In connection with the foregoing, high-quality fastening of the well is not ensured.

 As a prototype, the method of preparation of TP with B / C = 0.38-0.45 by dissolving C-3 superplasticizer in water in an amount of 0.30-0.50% by weight of cement and a modifying reagent - sulfacell in an amount of 0.40 was taken -0.60%, after which the resulting aqueous solution is mixed with cement Portland cement (see RF patent 2136843 from 04/28/97, CL E 21 B 33/138, publ. BI 25, 1999). The number of reagents used is recounted by the authors.

 The disadvantage of this method is the low quality of the fastening of wells due to the use of TP when cementing casing strings with insufficiently high basic physical and mechanical properties, during curing of which a weak cement stone with increased permeability and low adhesion to metal is formed. This is due to the following.

The joint dissolution in water of the S-3 superplasticizer and sulfacell and further mixing with grouting Portland cement leads to the fact that sulfacell creates hard-to-permeable shells on hard surfaces, which makes it difficult for the S-3 superplasticizer to access the cement grains, which is why the latter is not fully used . In addition, in the TR, chemical reactions primarily occur between the C-3 superplasticizer and cement Portland cement, after which a high molecular weight sulfacellum reagent is adsorbed on solid surfaces. The C-3 superplasticizer chemically interacts with the cations of divalent and trivalent metals of Portland cement with the replacement of the Na ⁺ cation of the C-3 oligomer with a cation of a divalent or trivalent metal. Due to this, the S-3 superplasticizer is quickly fixed on the solid surfaces of cement, and its non-polar (hydrophobic) part is turned towards the liquid phase. Sulfacell from the liquid phase is adsorbed on this surface and screens the hydrophobic part of the C-3 superplasticizer, reducing its plasticizing effect. Due to this, the hydration and hardening of Portland cement is slowed down, the setting time of TP increases. In addition, sulfacell increases the viscosity of the liquid phase. Therefore, the viscosity of the TP increases, which requires an additional increase in V / C. Thus, the efficiency of the reagents decreases, the setting time is slowed down and, as a result, the strength of the cement stone and its adhesion to metal and rock are reduced, which reduces the quality of the well fastening (see table 3).

The technical result that can be obtained by implementing the invention is reduced to the following:
the quality of well fastening is improved due to the use of TP when cementing casing strings with improved basic physical and mechanical properties, during curing of which a durable cement stone with low permeability and increased adhesion to metal is formed.

 The essence of the invention lies in the fact that in the method of preparing cement slurry by dissolving in water a modifying reagent and C-3 superplasticizer based on the sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde, followed by mixing with grouting Portland cement, a grouting solution with a water-cement ratio of 0.30-0 is prepared. 35, and as the modifying reagent, bottoms of monoethanolamine are used - a waste product for the purification of industrial gases by monoethanolamine in the production of ammonia (COMEA), which in an amount of 0.1-0.3% by weight of cement are dissolved in 90-92% of the total water and mixed with grouting Portland cement, followed by stirring the resulting suspension for 10-15 minutes, and C-3 superplasticizer in an amount of 0 , 7-1.5% by weight of cement is dissolved in the remaining water and mixed with the latter.

For the preparation of TR use:
VAT residues of monoethanolamine according to TU 6-02-18-8-74 of the following composition: monoethanolamine 40-55%, M- (2-hydroxyethyl) ethylenediamine 5-8%, oxosolidone-2 0.1-1%, 1- ( 2-hydroxyethyl) imidazolin-2 0.1-0.3%, unidentified organic substances 16.7%, water - the rest; S-3 superplasticizer according to TU 6-14-625-80, grouting Portland cement in accordance with GOST 1581-96.

As a result of mixing cement Portland cement with an aqueous solution of COMEA, the physicochemical and chemical processes of cement hydration are parallel: wetting of the cement powder with water, saturation of the liquid phase with calcium oxide hydrate, dissolution and hydration of clinker minerals of Portland cement, chemical interaction and adsorption of COMEA components (monoethanolamine, these oxosolidone and imidozolines) with grouting Portland cement, the formation of solvate shells and colloidal structures. At the same time, due to the influence of COMEA components, a rapid increase in the pH of TP occurs. This is due to the fact that the amines that make up COMEA are organic bases and can attach protons to their molecule, taking them, for example, from water with the formation of hydroxides
RNH ₂ + HOH -> R | NH ₃ | ⁺ OH ^-
Rapid pH increase favorably affects the hydration of grouting Portland cement, the dissolution and hydration of clinker minerals are accelerated and the solution is supersaturated with hydration products, primarily calcium hydroaluminates and hydroaluminoferrites, TP colloidation processes and the binding of gravitational water quickly occur, which contributes to its sedimentation stability, thixotropy and affects the quality of the wells.

On the other hand, KOMEA, in addition to monoethanolamine, also contains a significant amount of strong hydrophobizing components (oxosolidone, imidozoline, etc.), adsorbing on solid surfaces and hydration products of TP with its polar part, they are non-polar (hydrophobic) part facing the dispersion medium - liquid phase, which creates a plasticizing effect and prevents premature growth of crystals of hydration products. Additional mixing for 10-15 minutes contributes to a more complete and uniform throughout the volume of the above processes of hydration and colloidation of cement Portland cement and its dispersion. The resulting suspension of cement Portland cement with an aqueous solution of COMEA is mixed with an aqueous solution of C-3 superplasticizer. The latter primarily increases the volume of the liquid phase, which leads to an increase in the thickness of the liquid layer between the solvate shells and to an improvement in the ductility of the TP. In this case, the C-3 superplasticizer is consumed for interaction only with part of the solid surface of the TP, since most of it is blocked by water and the components of KOMEA dissolved in it. In this case, the C-3 superplasticizer interacts mainly with TP hydration products at the phase boundary. Chemical interaction of the C-3 superplasticizer oligomer with cations of divalent and trivalent metals occurs by replacing the Na ⁺ cation of the C-3 oligomer with Ca ²⁺ , Fe ²⁺ , A1 ^{3+ cations} , etc. Due to this, the polar part of the C-3 superplasticizer is turned to the solid phase, and non-polar (hydrophobic) - towards the dispersion medium, which provides TP with an additional plasticizing effect.

 Since the C-3 superplasticizer is not fixed on the entire solid surface of the dispersed phase of TP, but only on its part, its amount naturally increases per unit surface area. Together with the hydrophobic part of COMEA, this creates an additional plasticizing effect TP, which is prepared according to the proposed method. Increasing the ductility of the TP while maintaining the required consistency (spreadability of 18-20 cm) provides a decrease in W / C and an increase in its density.

 When TP hardens, a durable cement stone with low permeability and high adhesion to metal is formed. In borehole conditions TR is in constant motion throughout the entire cementing time. Thanks to the proposed method of preparation, the composition of the reagents receive TP with improved physical and mechanical properties, the forcing of which into the annular space occurs without additional resistance, the drilling fluid is completely displaced, and the TP is lifted over the entire cementing interval.

 After the end of the forcing, the liquid is intensively consumed for cement hydration. There is a rapid supersaturation of solutions and accelerated coagulation. This is greatly facilitated by the formation of complex amine hydroxides from COMEA. Solvation shells and a double electric layer of colloidal particles on cement hydration products are thinning. Intensive coalescence of crystals begins. This is also facilitated by the fact that at the stage of supersaturation of the liquid phase of the TP, the anions of the anionic surfactant - C-3 superplasticizer are neutralized by cations of the cationic surfactant - COMEA. This provides a more intensive coagulation of TP, an increase in thixotropy and acceleration of coalescence of crystals of hydration products of cement Portland cement.

 An increase in the coagulation rate (thixotropy coefficient) after the termination of the TP in the annulus is required in order to prevent channel formation in the TP during the waiting period for its solidification. During this period, the "active" pressure of the TP on the reservoir is reduced and gas from the reservoir can break through the liquid grouting ring upward, forming channels for fluid flow. Therefore, TP during this period should have sufficient plastic strength and have a high coagulation rate to prevent breakthrough of gas from the formation through the cement ring at the mouth.

 The preparation of TP with W / C less than 0.30 does not provide the required spreadability.

 The preparation of TR with W / C more than 0.35 is impractical, because there is an increase in spreadability greater than the required value, which leads to a significant water separation of TP, stratification and at the same time to an increase in the setting time.

 The content in TR COMEA in an amount of less than 0.1% by weight of cement leads to a decrease in the strength of cement stone and adhesion to metal.

 Content in TR KOMEA in an amount of more than 0.3% by weight of cement leads to a significant reduction in the setting time of TR, which does not allow for cementing work in the estimated time.

 The dissolution of COMEA in less than 90% of the total water amount with further mixing with grouting Portland cement leads to a decrease in flowability, and the fluidity of this suspension required for pumping is not ensured.

 The dissolution of KOMEA in more than 92% of the total amount of water with further mixing with cement Portland cement is impractical, because the rest of the water is insufficient for the complete dissolution of the superplasticizer C-3 in it.

 Stirring the suspension for 10 minutes does not provide a uniform value in terms of spreadability and density, and for more than 15 minutes is ineffective, because does not lead to further improvement of properties.

 The content of S-3 superplasticizer in TR in an amount of less than 0.7% by weight of cement does not provide the required TP spreadability, which impairs its properties.

 The content of S-3 superplasticizer in TR in an amount of more than 1.5% by weight of cement is impractical, because leads to an increase in spreadability, an increase in water separation and stratification of TP, which affects the quality of well attachment.

 An analysis of the inventive step showed the following.

 In the concrete mixture, Portland cement and aggregate are mixed, then they are injected with KOMEA water in order to accelerate hardening (AS USSR 773002 dated 01.24.79, class C 04 V 13/24, publ. BI 39, 1980 ); A known method of preparing a concrete mixture by mixing a binder and aggregates with a plasticizing additive, introduced together with part of the mixing water, with a hardening accelerator, introduced with the remaining mixing water, in which the hardening accelerator is introduced with 70-75% mixing water and mixed 1.5- 2 min, then plasticizing and air-entraining additives are introduced with the remaining mixing water and mixed for 1-1.5 min in order to increase the mobility of the concrete mixture, the strength of concrete and reduce the consumption of the components of the additive (see.a. USSR 833705 from 08.27.79 according to class C 04 B 13/22, publ. BI 20, 1981); use COMEA in the reagent for processing potassium drilling fluids in order to improve the structural and mechanical properties of drilling fluids (AS USSR 1116044 from 07.16.82, class C 09 K 7/02, BI 36, 1984); a superplasticizer is used in the polymer-mineral mixture — the product of the interaction of the bottom residue of the benzoic acid production stage with the oxidation of toluene in the production of caprolactam — X-oil with the bottom residue of the purification of the ammonia production system based on monoethanolamine and with the concentrated aqueous effluent — the waste product of caprolactam production from toluene based on the sodium salts of carboxylic acids with the aim of increasing mobility in the ratio by weight, respectively, 50: 11.5: 61.5 (see AS of the USSR 1728164 dated January 17, 1990, class C 04 B 26/12, publ. BI 15, 1992 .); polymer concrete mixture as an additive superplasticizer use the product of the interaction of 66.7 wt. % of the waste of caprolactam production from toluene based on “X-oil” carboxylic acids from 33.3 wt.% COMEA in order to increase workability (a. from the USSR 1724624 dated 03.03.90, class C 04 B 26/12, publ. BI 13, 1992); surface-active additive to cement, including lignosulfonates and an amine-containing substance, with the aim of regulating the particle size distribution of cement and increasing the plasticity of the cement mortar (see a.s. of the USSR 631483 dated 04/11/77, class C 04 B 7/35, 13 / 24, publ. BI 41, 1978). Based on the foregoing, we have not identified technical solutions that are based on features that completely coincide with the distinctive features of the claimed technical solution. The latter does not follow explicitly from the analyzed prior art, i.e. has an inventive step.

 In more detail the essence of the proposed method is illustrated by the following examples.

Example 1
To prepare a TP with W / C = 0.30, 1000 g of grouting Portland cement and 300 ml of water are used.

 Dissolve COMEA in an amount of 1.0 g (which is 0.1% by weight of cement) in 270 ml of water (which is 90% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 10 minutes. In the remaining 30 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. The spreadability, density, setting time, and water yield of the TR are determined in accordance with GOST 26 798.1-96. Determine the plastic viscosity, static shear stress (SSS) after 1 and 10 minutes, the thixotropy coefficient. The rest of the solution is poured into standard forms and left in the thermostat for 24 hours for curing. Hardened samples are tested for strength, adhesion, gas permeability.

TP and cement stone have the following properties:
spreadability - 18.0 cm, density - 2115 kg / m ^3, the start setting - 1 h 45 min, the end of the setting - 3 h 05 min, water yield - 28.2 cm ^3/30 min, the plastic viscosity - 115 mPa • s, SNA in 1 min - 112 dPa, in 10 min - 255 dPa, thixotropy coefficient - 2.28, water separation is absent, cement stone bending strength - 8.5 MPa, adhesion to metal - 2.72 MPa, gas permeability coefficient - 0.324 • 10 ^-3 μm ² . Fishing example.

 Well 32 of the Kuryinsky field, Komi Republic, prospecting, vertical.

Initial data:
Production string - 168 mm
Depth of descent of the production casing - 1450 m
Reservoir pressure - 27.3 MPa
The temperature at the bottom - 32 ^o C
According to the guidelines for the selection of grouting materials and solutions (see RD 39-00147001-767-2000, Instructions for attaching oil and gas wells, M., Nedra, 2000, pp. 137-141), the required volume of TR, taking into account the cavity cavernosity, is
V _Tr = 18 m ³ .

где ρ_тр - плотность ТР, кг/м³;
Р_пл - пластовое давление, МПа;
g - ускорение свободного падения, м/с²;
Н - глубина спуска эксплуатационной колонны, м,

Определяют выход ТР, получаемого из 1000 кг тампонажного портландцемента

где В/Ц - водоцементное отношение ТР, 0,35,

На 1 м³ ТР количество тампонажного портландцемента G_тпц составляет
G_ТПЦ=1/0,67=1,49 т,
для приготовления 18 м³ ТР количество тампонажного портландцемента
G_1ТПЦ=k•G_ТПЦ•V_тр,
где k - коэффициент запаса, учитывающий потери цемента на отсев при загрузке и распыление при загрузке и затворении, 1,05,
G_1ТПЦ=1,05•1,49•18=28,16 т,
объем воды

Для приготовления ТР с ρ_тр=2015 кг/м³, значением В/Ц=0,35 используют:
суперпластификатор С-3 в количестве 0,7% от массы цемента, расход которого составляет
Q_С-3=0,7•28,16/100=0,197 т,
КОМЭА в количестве 0,1% от массы цемента, расход которых составляет
Q_КОМЭА=0,1•28,16/100=0,028 т.The required density TR ρ _tr determined by the formula

where ρ _Tr - density TR, kg / m ³ ;
P _PL - reservoir pressure, MPa;
g is the acceleration of gravity, m / s ² ;
N - the depth of descent of the production casing, m,

Determine the yield of TP obtained from 1000 kg of cement Portland cement

where W / C - water-cement ratio TP, 0.35,

On 1 m ³ TP the amount of cement Portland cement G _tpc is
G _TPC = 1 / 0.67 = 1.49 t,
for the preparation of 18 m ³ TP the amount of cement Portland cement
G _1TPC = k • G _TPC • V _tr ,
where k is the safety factor taking into account the loss of cement on screening when loading and spraying when loading and mixing, 1.05,
G _1TPC = 1.05 • 1.49 • 18 = 28.16 t,
water volume

To prepare a TR with ρ _tr = 2015 kg / m ³ , a value of B / C = 0.35 use:
superplasticizer C-3 in the amount of 0.7% by weight of cement, the consumption of which is
Q _C-3 = 0.7 • 28.16 / 100 = 0.197 t,
COMEA in the amount of 0.1% by weight of cement, the consumption of which is
Q _COMEA = 0.1 • 28.16 / 100 = 0.028 t.

0.028 tons of COMEA (0.1% by weight of cement) are dissolved in 8.87 m ^{3 of} water (90% of the total water) and mixed with 28.16 tons of grouting Portland cement. To do this, use the cementing unit CA-320M and cement-mixing machine SM-20. The resulting suspension is pumped into an averaging tank with a volume of 20 m ³ , where it is further mixed for 15 minutes.

Dissolve 0.197 tons of C-3 superplasticizer (0.7% by weight of cement) in the remaining water — 0.98 m ^3, and this solution is introduced into an averaging tank, where it is further mixed with the suspension located there. Spreadability TP is 19 cm.

 TP is pumped into the well, forced into the annulus and the well is left for 24 hours.

 Geophysical studies have established: tightness of the casing string, rise of the solution over the entire cementing interval, good cementing quality.

Example 2
To prepare a TP with W / C = 0.30, 1000 g of grouting Portland cement and 300 ml of water are used.

 Dissolve COMEA in an amount of 2.0 g (which is 0.2% by weight of cement) in 270 ml of water (which is 90% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 12 minutes. In the remaining 30 ml of water, superplasticizer C-3 is dissolved in an amount of 11.0 g (which is 1.1% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 20.5 cm, density - 2115 kg / m ^3, the start setting - 1 h 57 min, the end of the setting - 2 h 55 min, water yield - 20.0 cm ^3/30 min, the plastic viscosity - 117 mPa • s, SNA after 1 min - 86 dPa, after 10 min - 236 dPa, thixotropy coefficient - 2.74, water separation is absent, cement stone bending strength - 8.7 MPa, adhesion to metal - 2.78 MPa, gas permeability coefficient - 0.256 • 10 ^-3 μm ² .

Example 3
To prepare a TP with W / C = 0.30, 1000 g of grouting Portland cement and 300 ml of water are used.

 Dissolve COMEA in an amount of 3.0 g (which is 0.3% by weight of cement) in 273 ml of water (which is 91% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 27 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 19.0 cm, density - 2115 kg / m ^3, the start setting - 1 h 30 min, the end of the setting - 1 h 50 min, water yield - 24.8 cm ^3/30 min, the plastic viscosity - 127 mPa • s, SNS after 1 min - 125 dPa, after 10 min - 363 dPa, thixotropy coefficient - 2.90, water separation is absent, cement stone bending strength - 9.2 MPa, adhesion to metal - 2.96 MPa, gas permeability coefficient - 0.196 • 10 ^-3 μm ² .

Example 4
To prepare a TP with W / C = 0.30, 1000 g of grouting Portland cement and 270 ml of water are used.

 Dissolve COMEA in an amount of 3.0 g (which is 0.3% by weight of cement) in 276 ml of water (which is 92% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 24 ml of water, superplasticizer C-3 is dissolved in an amount of 15.0 g (which is 1.5% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 21.5 cm, density - 2115 kg / m ^3, the start setting - 2 h 10 min, the end of the setting - 2 h 40 min, water yield - 11.8 cm ^3/30 min, the plastic viscosity - 118 mPa • s, SNA after 1 min - 148 dPa, after 10 min - 474 dPa, thixotropy coefficient - 3.20, water separation is absent, cement stone bending strength - 8.8 MPa, adhesion to metal - 2.83 MPa, gas permeability coefficient - 0.188 • 10 ^-3 μm ² .

Example 5
To prepare a TP with W / C = 0.32, 1000 g of grouting Portland cement and 320 ml of water are used.

 KOMEA is dissolved in an amount of 1.0 g (which is 0.1% by weight of cement) in 288 ml of water (which is 90% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 10 minutes. In the remaining 32 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 18.0 cm, density - 2080 kg / m ^3, the start setting - 1 h 55 min, the end of the setting - 2 h 55 min, water yield - 32.5 cm ^3/30 min, the plastic viscosity - 112 mPa • s, SNA after 1 min - 94 dPa, after 10 min - 212 dPa, thixotropy coefficient - 2.25, water separation is absent, cement stone bending strength - 8.3 MPa, adhesion to metal - 2.48 MPa, gas permeability coefficient - 0.368 • 10 ^-3 μm ² .

Example 6
To prepare a TP with W / C = 0.32, 1000 g of grouting Portland cement and 320 ml of water are used.

 Dissolve COMEA in an amount of 2.0 g (which is 0.2% by weight of cement) in 288 ml of water (which is 90% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 12 minutes. In the remaining 32 ml of water, superplasticizer C-3 is dissolved in an amount of 11.0 g (which is 1.1% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 18.5 cm, density - 2080 kg / m ^3, the start setting - 2 h 10 min, the end of the setting - 3 h 00 min, water yield - 23.4 cm ^3/30 min, the plastic viscosity - 114 mPa • s, SNA after 1 min - 84 dPa, after 10 min - 220 dPa, thixotropy coefficient - 2.62, water separation is absent, cement stone bending strength - 8.4 MPa, adhesion to metal - 2.46 MPa, gas permeability coefficient - 0.320 • 10 ^-3 μm ² .

Example 7
To prepare a TP with W / C = 0.32, 1000 g of grouting Portland cement and 320 ml of water are used.

 KOMEA is dissolved in an amount of 3.0 g (which is 0.3% by weight of cement) in 291.2 ml of water (which is 91% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 28.8 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 19.0 cm, density - 2080 kg / m ^3, the start setting - 1 h 40 min, the end of the setting - 2 h 20 min, water yield - 26.5 cm ^3/30 min, the plastic viscosity - 123 mPa • s, SNA after 1 min - 103 dPa, after 10 min - 288 dPa, thixotropy coefficient - 2.80, water separation is absent, cement stone bending strength - 8.7 MPa, adhesion to metal - 2.87 MPa, gas permeability coefficient - 0.286 • 10 ^-3 μm ² .

Example 8
To prepare a TP with W / C = 0.32, 1000 g of grouting Portland cement and 320 ml of water are used.

 Dissolve COMEA in an amount of 3.0 g (which is 0.3% by weight of cement) in 294.4 ml of water (which is 92% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 25.6 ml of water, superplasticizer C-3 is dissolved in an amount of 15.0 g (which is 1.5% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 20.0 cm, density - 2080 kg / m ^3, the start setting - 2 h 15 min, the end of the setting - 2 h 50 min, water yield - 14.4 cm ^3/30 min, the plastic viscosity - 118 mPa • s, SNA after 1 min - 132 dPa, after 10 min - 396 dPa, thixotropy coefficient - 3.00, water separation is absent, cement stone bending strength - 8.4 MPa, adhesion to metal - 2.45 MPa, gas permeability coefficient - 0.274 • 10 ^-3 μm ² .

Example 9
To prepare a TP with W / C = 0.35, 1000 g of grouting Portland cement and 350 ml of water are used.

 Dissolve COMEA in an amount of 1.0 g (which is 0.1% by weight of cement) in 315 ml of water (which is 90% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 10 minutes. In the remaining 35 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 19.0 cm, density - 2015 kg / m ^3, the start setting - 2 h 10 min, the end of the setting - 3 h 10 min, water yield - 36.7 cm ^3/30 min, the plastic viscosity - 108 mPa • s, SNA after 1 min - 75 dPa, after 10 min - 165 dPa, thixotropy coefficient - 2.20, water separation is absent, cement stone bending strength - 8.1 MPa, adhesion to metal - 2.24 MPa, gas permeability coefficient - 0.410 • 10 ^-3 μm ² .

Example 10
To prepare a TP with W / C = 0.35, 1000 g of grouting Portland cement and 350 ml of water are used.

 Dissolve COMEA in an amount of 2.0 g (which is 0.2% by weight of cement) in 318.5 ml of water (which is 91% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 12 minutes. In the remaining 31.5 ml of water, superplasticizer C-3 is dissolved in an amount of 11.0 g (which is 1.1% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 20.0 cm, density - 2015 kg / m ^3, the start setting - 2 h 15 min, the end of the setting - 3 h 05 min, water yield - 26.8 cm ^3/30 min, the plastic viscosity - 112 mPa • s, SNA in 1 min - 81 dPa, in 10 min - 203 dPa, thixotropy coefficient - 2.50, water separation is absent, cement stone bending strength - 7.9 MPa, adhesion to metal - 2.15 MPa, gas permeability coefficient - 0.380 • 10 ^-3 μm ² .

Example 11
To prepare a TP with W / C = 0.35, 1000 g of grouting Portland cement and 350 ml of water are used.

 Dissolve COMEA in an amount of 3.0 g (which is 0.3% by weight of cement) in 322 ml of water (which is 92% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 28 ml of water, superplasticizer C-3 is dissolved in an amount of 7.0 g (which is 0.7% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 21.0 cm, density - 2015 kg / m ^3, the start setting - 1 h 55 min, the end of the setting - 2 h 45 min, water yield - 28.0 cm ^3/30 min, the plastic viscosity - 119 mPa • s, SNS after 1 min - 81 dPa, after 10 min - 219 dPa, thixotropy coefficient - 2.70, water separation is absent, cement stone bending strength - 8.2 MPa, adhesion to metal - 2.29 MPa, gas permeability coefficient - 0.375 • 10 ^-3 μm ² .

Example 12
To prepare a TP with W / C = 0.35, 1000 g of grouting Portland cement and 350 ml of water are used.

 Dissolve COMEA in an amount of 3.0 g (which is 0.3% by weight of cement) in 322 ml of water (which is 92% of the total amount of water). The resulting solution is mixed with 1000 g of cement Portland cement. Next, the resulting suspension is stirred for 15 minutes. In the remaining 28 ml of water, superplasticizer C-3 is dissolved in an amount of 15.0 g (which is 1.5% by weight of cement). Then this solution is mixed with a previously prepared suspension until a homogeneous TP. Then carry out all operations, as indicated in example 1.

TP and cement stone have the following properties:
spreadability - 22.0 cm, density - 2015 kg / m ^3, the start setting - 2 h 25 min, the end of the setting - 3 h 00 min, water yield - 16.9 cm ^3/30 min, the plastic viscosity - 117 mPa • s, SNA after 1 min - 115 dPa, after 10 min -327 dPa, thixotropy coefficient - 2.80, water separation is absent, cement stone bending strength - 8.0 MPa, adhesion to metal - 2.06 MPa, gas permeability coefficient - 0.360 • 10 ^-3 μm ² .

 Compared with the sources of fame specified in the section "prior art", the inventive method for the preparation of cement slurry is patentable, because it meets the conditions of novelty, inventive step and industrial applicability.

 Note.

 Tests of grouting mortar and cement stone were carried out according to GOST 26 798.1-96 "Cement grouting. Test methods".

The setting time of the cement slurry and the strength of the cement stone during bending was determined at a temperature of 75 ^about C, a pressure of 0.1 MPa. The setting time was determined on a Vika device, strength - on MII-100.

 The adhesion of cement stone to metal was determined by extruding a cement sample with a height and diameter of 40 mm from a steel holder.

 The gas permeability of cement stone was determined on the installation of GK-5.

 The spreadability of the cement slurry was determined by the cone of AzNII.

Fluid loss of cement slurry was measured on the instrument BM-6 at a pressure drop of 0.1 MPa and a temperature of 22 ° ^C.

 Plastic viscosity and static shear stress were determined on a Baroid rotary Fann viscometer.

In cement slurries prepared according to the claimed method, table 1 p / p 1-12, 14-21, no water separation, in p / n 13, 22 - water separation of 2 to 3 cm ³ .

The water separation of cement slurries prepared by the prototype method, respectively, in order 1 - 1.55 cm ³ , order 2 - 0.48 cm ³ , order 3 - 0.50 cm ³ .

The setting time of the cement slurry-analogue was determined at a temperature of 20 ^about C.

 * The spreadability of the suspension after additional mixing was 15 cm

 ** The spreadability of the suspension after additional mixing was 18 cm.

 *** The spreadability of the suspension after additional mixing was 16 cm.

 **** When dissolving the S-3 superplasticizer in the remaining water, its incomplete dissolution was observed - the precipitate was up to 2% by weight.

Claims (1)

 A method of preparing a grouting mortar by dissolving in water a modifying reagent and C-3 superplasticizer based on the sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde, followed by mixing with grouting Portland cement, characterized in that a grouting mortar with a water-cement ratio of 0.30-0.35 is prepared, and as a modifying reagent, bottoms of monoethanolamine are used - a waste from the purification of technical gases by monoethanolamine in the production of ammonia, which in an amount of 0.1-0.3% of ma cement sands are dissolved in 90-92% of the total water quantity and mixed with grouting Portland cement, followed by stirring of the resulting suspension for 10-15 minutes, and C-3 superplasticizer in the amount of 0.7-1.5% by weight of cement is dissolved in the remaining water and mixed with the latter.

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