SU1745893A1 - Composition for producing aerated grouting mortar - Google Patents

Abstract

The aerated cement slurry is used for cementing wells with low density portland cement in normal geological conditions and in the presence of anomalously low pressure zones. It contains, by weight.h .: portland cement 100; ethoxylated monoalkylphenols of propylene trimers with degree of ethoxylation of 12 neonol AF 9-12, water-glycol mixture 0.1-1.4; air 0.01-0.02 and water 45-80. 3 tab.

Description

 The invention relates to the field of well casing and can be used in well cementing with low density density portland cement raters both under normal geological conditions and in the presence of abnormally low pressure zones.

It is known to use surface-active substances (surfactants) as emulsifiers-foaming agents of aerated cement mortars.

It is known to use in aerated cement solutions of non-ionic surfactants that are resistant to salinity, in particular, OP g-10, which is a mixture of cocoalkylphenyl ethers of polymethyl glycol based on polymeric distillate with a degree of ethoxylation 10.

Chemical formula OP-10

Oh-oh (sn2-n: n2) 10n t o. .

 To

ate with you

Gs

OP-10 is soluble in water, including reservoir; but does not dissolve in hydrocarbons. In this case, dissolution in water under normal conditions is prolonged (within 2–3 hours), or to accelerate the process it is necessary to heat the water to 50 ° C; pour point 5-10 ° C

The use of OP-10 in an amount of 0.05-0.5% by weight of cement in combination with aeration allows to obtain a foam-cement solution with a density of 800-1300 kg / m3.

However, in a number of cases (under the conditions of LNPD, the presence of poorly cemented rocks, with small annular gaps in the well, etc.), cementing solutions with lower density must be used for cementing the columns.

It is known to use an aerated portland cement solution using 0.1-0.5% DPD-1 as a blowing agent, which is a mixture of non-ionic surfactant sodium alkylphenylethoxy sulfate

0 () ft-0-S02ONa О

and

20

and disodium alkylphenyl sulfonate ethoxy sulfate

R Yro (cH2 - cH2} rro-so2ONa

S02ONa °

25

thirty

The use of DPD-1 allows to obtain a cement slurry density in the range of 300-480 kg / m3.

Known aerated solution has the following disadvantages.

Its application in Western Siberia showed that the success of cementing operations is 80%. Cementing on wells with zones of catastrophic absorption was unsuccessful. This is because the density of the cement slurry is not low enough. To prevent the absorption of aerated cement slurry and to increase the success of cementing operations in particularly difficult geological conditions, it is necessary to reduce its density by increasing air absorption.

Surfactant. Used in a known composition, it is difficult to dissolve in water, especially at low temperatures. As a result of this, the technological process of preparing an aerated thermal solution in the wells becomes much more complicated: additional equipment is needed for heating and mixing, a considerable investment of time and labor of the operating personnel.

A significant drawback of the composition is the lack of industrial production.

DPD-1, which makes its widespread use impossible. The industrial production of this surfactant is not planned in the coming years due to the lack of initial synthesis products.

The purpose of the invention is to expand the range of densities of aerated cement slurry, simplify the technology of its preparation and increase the success of well cementing.

The goal is achieved by the fact that the composition for preparing an aerated cement slurry, including Portland cement, a foaming agent, air and water, contains non-ionic surfactants Neonol AF 9-12 - ethoxylated propylene monomethylalkyl phenols with a degree of hydroxyethyl plating and a process technology as a blowing agent with a degree of oxyethylation of 12 and a process technology. oligomers (for example, oligoester acrylates, oligoesters, etc.) - water-glycol mixture in the following ratio of components, parts by weight:

Portland Cement100

Neol AF 9-12 hydroxyethylated monoalkyl-phenols of propylene trimers with a degree of hydroxyethylation of 12.0.2-0.6

Water-glycol mixture 0.1-1.4

Air 0,01-0,02

. Water 45-60

moreover, water-glycol mixture contains monoethylene glycol. ethyl cellosolve. diethylene glycol. triethylene glycol. ethylcarbolol and water in the following ratio, wt.%:

27-35

27-35

5-8

2-5

5-8

Rest

Neonol AF 9-12 - new domestic reagent. The neonol has an average molecular weight of 748–30 units. Appearance - clear, oily liquid from colorless to light yellow color, with a density of 1.045 g / cm3.

Chemical formula P-SeNU (C2H iO) i2H. where R is a branched alkyl radical (isononyl). Soluble in water and organic solvents. Neonol LF 9-12 is a highly effective surfactant used as an emulsifier, wetting agent and for other

leu in a number of industries. It is a non-volatile product with a boiling point above 280 ° C. According to the degree of exposure to a person, it is classified as hazard class 3. Organic characteristics: for household water bodies of 0.1 mg / dm3, for fisheries of 0.25 mg / dm3.

Due to the higher degree of oxyethylation, neonol AO 9-12 has a higher thermal stability and can work while retaining the full range of properties (including emulsifying, foaming, stabilizing) at temperatures up to 130 ° C. This reagent is not deficient, which is why its use or compositions based on it are promising in the oil industry.

The research results (Table 1. p. 4-9) showed that neonol AF 9-12 is an effective foaming agent for cement slurries, but it does not improve the air-entraining ability of the cement slurry as compared to the known (paragraphs 1-3).

Achieving the goal provides neonol AF 9-12, a modified water-glycol mixture (HCV). HCV itself does not have any foaming ability in the medium of cement mortar (Table 1, p. 10-11). The improvement in the foaming properties of α-neonol AF9-12 by the modification of HCV is explained by the synergistic effect (Table 1, p. 17-20), which makes it possible to obtain an aerated solution with a density of 240-390 kg / m3.

The water-glycol mixture is a technological waste of oligomer production, non-volatile, non-recyclable and, according to the technological procedure of production, destroyed in incineration furnaces. The volume of waste is in the order of 1000 tons / year. The substances included in the composition of the water-glycol mixture are monoethylene glycol. diethylene glycol. triethylene glycol, ethylene carbitol, ethyl cellosolve - used in the preparation of organic synthesis products, in particular oligomers such as oligo ether scrylates, oligoesters, etc. The water-glycol mixture is formed as a result of cleaning equipment, tanks, tanks, pipelines used for these substances.

The water-glycol mixture may have a different composition. The effectiveness of the recommended ratio of HCV components is indicated by the results of studies conducted in HCV of various compositions (see Table 2).

The recipe given in paragraph 15 of table. 1, includes B GS composition 1, VP. 16-HCV composition 3. When comparing the solution densities under paragraph 15-17, it is clear that the proposed HCV composition is most effective (paragraph 17).

According to their chemical structure, these substances are mainly alcohols (monoethylene glycol, diethylene glycol, triethylene glycol, ethyl carbitol), and ethyl cellosolve — simple ether (ethylene glycol monoethyl ether). Both classes

10 compounds (alcohols and ethers) have surface-active properties and are referred to as non-ionic surfactants.

The water-glycol mixture mixes well with water and neonol AF 9-12.

15 Brief description of substances that are part of the water-glycol mixture.

Monoethylene glycol - HOSISCH OH is colorless low viscosity liquid with a density of 1.113 g / cm3. .6 ° C. .3 ° C.

0 mixed with water, alcohols, etc

Ethyl cellosolve - C2HsOC2H40H is a colorless low viscosity liquid with a density of 0.931 ,, 60 ° C, tnn -70 ° C, soluble in water and organic solvents.

5 Diethyl glycol - (HOChtoCf hO - colorless low viscosity liquid with a density of 1.1 g / cm3. T ,, 8 ° C, well soluble in water and organic solvents.

0 Triethylene glycol - НО-СН2-СН2-0-СН2СН2-0-СН2 СН2-ОН - is non-volatile non-volatile LIQUID. Tsamov ignition of 371 ° C.

Ethylcarbitol - C2Hs-OCH2-CH2 0-CH2-OH is a slightly yellow liquid,

5, the ignition temperature range is 97-112 ° C, it is infinitely mixed with water, soluble in organic solvents.

All named substances are according to

0 GOST 12.1.007-76 refers to the 3rd class of danger.

Possessing antifreeze properties, the water-glycol mixture prevents neonol from freezing at low temperatures of 5 pax. In tab. 3 shows the freezing point of solutions of neonol AF 9-12 in the water-glycol mixture. t, f,

The use of the proposed combination of reagents makes it almost instant.

0 the process of dissolution of neonol in water at both positive and negative temperatures, as a result of which the technology of preparation of aerated cement slurries is greatly simplified

5 suspensions, especially at low temperatures.

In comparison with the known, the time spent on preparing the solution is significantly reduced, the need for heating and the use of additional equipment and tools is eliminated.

As can be seen from the data table. 1. The aerated portland cement solution prepared with the use of neonol AF 9-12 modified with an aqueous glycol mixture as a blowing agent is characterized by more efficient foaming, while the density range of the resulting solution is expanded compared with the known (see Table. 1, p. 1-2, 17-20). Cement stone is not inferior in strength properties obtained by known recipes.

Aerated cement slurry has a 100% stability, which characterizes its high stability over time. Stability was determined in accordance with RD 2-1232-84.

The strength characteristics of p. 4-16 and table 22. 1 is not shown because their respective compositions are shown to prove the effectiveness of the proposed composition in comparison with the known 25 solution and each of the components (neonol, HCV) separately, as well as the effectiveness of the selected ratios, namely one neonol AF 9-12 does not significantly reduce the density compared to a known solution (see Tables 1 pp. 1-3 and 4-9), and when only HCV is introduced into the cement slurry, no foaming is observed at all (p. 10 -eleven); The composition according to claim 12 has a high density compared to 35 known (1600 kg / m due to insufficient aeration (air content is 0.005 parts by weight per 100 msec. of cement)): the composition according to paragraph 13 shows that it is not appropriate to increase the air content to 0.025 parts by weight by 40 100 parts by weight of cement: the composition according to claim 14 is beyond the limit of HCV: the composition according to claim 14 is beyond the limit of HCV: due to insufficient HCV content, the density does not decrease by 45 compared with the known: composition on p. 22

- It has a high density (1100 bonds with insufficient amount of a mixing fluid and also does not correspond to the goal.

In tab. 1 shows the amount of air that is supplied to the cement slurry y may be involved in the structure of the resulting aerated system. Factors such as a given air flow rate. 55 the rotation speed of the stirrer, the dimensions of the installation, etc., were kept strictly constant during the experiments. However, it is known that the actual air content in the system depends not only on

the amount of injected air, but also on the amount of structural agents used — surface-active components, in particular, neonol AF 9-12 and HCV. This is confirmed by tabular density data. Thus, in paragraphs 14 and 17 with the same amount of air introduced into the system (0.02 parts by weight). but different amounts of surfactant injected (0.25 msec. hours in paragraph 14 and 0.4 May. of hours in paragraph 17), the density of the solutions are different.

The selection of formulations is carried out as follows.

The amount of neonol AF 9-12 is determined by the efficiency of air entrapment with a Portland cement mortar and a decrease in its density.

The ratio of components in the water-glycol mixture is determined by the specifics of the technological operations for cleaning and washing equipment, etc.

The ratio of neonol AF 9-12 and the water-glycol mixture is found empirically. in order to achieve a higher foaming efficiency in the aerated Portland environment. entant solution and to ensure the expansion of the range of densities in comparison with the known without deteriorating the strength characteristics of the resulting stone.

The required water-cement ratio was found taking into account the ability of the cement slurry to efficient foaming in the presence of the reagents used, as well as the sedimentation stability of the resulting aerated foam cement system and the strength characteristics formed under standard and thermo-insulating tampon stone.

The amount of air supplied is determined taking into account the ability to foam cement and to reduce its density.

Portland cement solution is aerated using a compressor unit with controlled air flow.

The control of the density of the resulting solution is carried out by the pycnometric method.

Measurement of strength. Cement stone is made by standard methods.

EXAMPLE 1: A hamperage solution is prepared in accordance with paragraph 17 of the Table. 1. containing mps.ch. (d):

100 0.2

(300) (0.6)

0.2 60

(0.6) (180)

For this, 0.6 g of nsonol and 0.6 g of HCV are mixed. get the mixture. In a water of 180 g in the amount of 180 g of cement and 300 g of cement and mixed in a spherical bowl for 3 minutes. Mixture 1 is introduced into the resulting cement slurry and, after mixing, for 3 minutes, the cement slurry is aerated in a laboratory setup in accordance with RD 2-1232-84 with air supply corresponding to 0.02 wt.h. The density of the resulting foamed psglandtsentny solution of 390 kg / m3. Stability of a pszvvor of 100%. After 43 h, the cement stone formed from this solution has the following characteristics: at and, 1 MPa Oii3r 1.0 MPz. , 2 MPa; at and MPa .5 MPa. , 3 MPa.

Pr and m e r 2. Prepare a solution in accordance with p. 18 of the Table. 1, containing, by weight.h. (d):

 Portland Cement100 (300)

NeonolAF9-120.3 (0.9)

HCV ..0.2 (0.6)

 Water45 (135)

The aerated cement slurry is prepared in the sequence indicated in Example 1 with an air supply corresponding to 0.01 wt.h. The density of the resulting solution is 280 kg / m3. Resistance 100%. A tampon stone formed from this solution, after 48 hours, has the following characteristics: 22 ° Cyr 0.1. MPa and “g MPa. .2 MPa: at and MPa .2 MPa,, 2 MPa.

PRI me R 3. Prepare a solution in accordance with p. 20 of the table. 1, containing, May. h (g):

Portland Cement100 (300)

NeonolAF9-120.6 (1.8)

HCV. 1.4 (4.2)

Water 50 (150)

50

The aerated cement slurry is prepared in the sequence indicated in Example 1. With air supplied at 0.02 wt.h. Density received

solution of 240 kg / m3. Resistance 100%. The grouting stone formed from this solution after 48 hours has the following characteristics: at and .1 MPa 55

(.8 MPa. .2 MPa: at and MPa, 8 MPs. Sgsszh 4.8 MPa.

5 10 15 20

five

0 5 .6

0

five

0

five

The advantages of the proposed composition for the preparation of the aerated solution therein the following are as follows.

The application of the proposed reagents allows, with effective foaming in the medium of aerated portland cement mortar, to significantly expand the density range and simplify the technology of its preparation, j

At the same time, it will be possible to solve the problem of utilization of technological waste from the production of oligomers. owned by the same company that produces neonol AF 9-12, exclude its incineration and associated costs and contribute to environmental improvement.

Cementing wells using the proposed composition for preparing an aerated cement slurry avoids fracturing in abnormally low pressure areas, eliminating the occurrence of absorption zones, avoiding the associated large material and labor costs for their elimination, improves the quality of cementing operations, and ensures recovery cement to the wellhead in difficult geological conditions.

Claims (1)

Invention Formula A composition for the preparation of an aerated cement slurry comprising portland cement, a foaming agent, air and water, characterized in that. what. in order to expand the density range, simplify the solution preparation technology and increase the success of well cementing, it contains non-ionic surfactants neonol AF 9-12 as foaming agent, ethoxylated propylene monomerphenols with propylene trimers with degree of ethoxylation 12, water-glycol mixture and technological waste production of oligomers in the following ratio of components, May .:: fe Portland Cement100 Neonol AF 9-12 hydroxyethylated monoalkylphenols of propylene trimers with a degree of hydroxyethylation of 120.2-0.6 Water-glycol mixture of 0.1-1.4 Air 0.01-0.02 Water45-60 moreover, in one glycol mixture, monoethylene glycol, ethyl cellosolve, diethylene glycol are contained. triethylene glycol. ethylcarbolol and water in the following ratio of components, May .: Monoethylene glycol 27-35 5 27-35 5-8 2-5 5-8 Else Glycolic esters ) The proposed composition of the HCV. table 2 Table 3