Grouting composition. RU patent 2244804.

FIELD: oil and gas production.

SUBSTANCE: invention provides grouting composition intended for selective insulation of water inflows into wells, including those occurring under low-temperature and high-permeation oil reservoirs, as well as for suppressing lost-circulating zones and brine inflow zones. Composition including product of hydrolytic etherification of chlorine-containing phenyltrichlorosilane still residues with aqueous alcohol solution contains, more specifically, product obtained by hydrolytic etherification of 100 wt parts of indicated residues with 10-32,8 wt parts of 90-93% aqueous alcohol solution in presence of 10-40 wt parts of orthosilicic acid ethyl ester and, additionally, 15-35 wt parts of chlorine-containing phenyltrichlorosilane still residues at summary content of the two components 133.2-161.6 wt parts. Grouting composition may further contain up to 16.8 wt parts of polar solvent.

EFFECT: lowered repair operation cost, enabled utilization in a wide formation temperature range, including that in high-permeation and low-temperature oil reservoirs, and prolonged shelf time of grouting composition.

2 cl, 1 tbl

The invention relates to the field of oil and gas industry and can be used for the selective isolation of the water in the well, including in conditions of low temperature and high permeability reservoirs, as well as to eliminate areas of acquisitions and rudoproyavlenii. Known composition based on Olkiluoto ester organosilicone compounds and polar solvent in which it is proposed to use one - or diatomic alcohols, or esters, or ketones (RU # 2066734, E 21 IN 33/138, publ. 20.09.96). This composition is suitable for wells with high formation temperatures (over 150°C), which is ensured by the absence of a catalyst for curing. For conditions of low (20-40°C) and moderate reservoir temperatures (50-60°C) no catalyst is the cause of too slow of a reaction of hydrolysis of taksigrup and further polycondensation of the resulting silanols. Curing of the composition occurs only under the influence of water remaining in the pores of the reservoir after its passage, the quantity of water is insufficient to ensure full curing of the composition, and pre-commissioning of water to obtain a slurry composition prior to injection into the well is undesirable, as it significantly affects the strength characteristics of the forming polymer. Known composition for the isolation of water-producing intervals of oil and gas reservoirs, consisting of oligoorganosiloxanes content of 9-11% hydrolyzable chlorine (US-USSR №945393). The presence of active chlorine is needed to build the capacity of the curing composition. However, this structure has several disadvantages: 1. From hydrolyzable group consists only of the chlorine group on communication ~Si-Cl. Is very aggressive: unmanaged hydrolysis and fast curing under the action of water, high corrosivity (emphasis Hcl even when in contact with air), difficulties with transport (swelling of the packaging), etc. 2. The reduction of the content of hydrolyzable chlorine is impossible to obtain a crosslinked product structure, i.e. its full curing. The growth of active groups chlorine creates conditions too fast-curing composition and the inability to upload it in water reservoir. In addition, because of the content easy hydrolysable chlorine impossible dilution water before injection into the well in order to obtain slurry composition and curing in the whole volume. 3. For the formation of a solid product in the whole volume of the composition should be water content of not less than 30%. However, in the reservoir are not created conditions for getting so much water in the composition, because when its injection into the reservoir is piston displacement of water and only a very small amount of the composition reacts with water. And formed in the contact zone of the polymer is virtually waterproof, so the process of hydrolysis will not extend into the composition. As a result, as shown, when the completion is the removal of the uncured product, resulting in failure to obtain the effect of the water shut-off or nedolgovremennogo. Known grouting composition comprising Olkiluoto ether articlenews acid, a polar solvent (from a number of alcohols, esters, ketones) and catalyst, and the solvent and the catalyst are in the amount of 10-200 and 1-10 parts by weight respectively per 100 parts by weight of the specified organosilicon (RU # 2144607, E 21 IN 43/32, publ. 20.01.2000). The composition is primarily intended to increase the period of loss of fluidity of the composition during its injection into low permeability reservoirs and at high formation temperatures, which is achieved by entering in the composition of the polar solvent. However, this structure also has a number of significant drawbacks. From hydrolyzable groups, providing cross-linking and curing of the composition, there are only ethoxyline group ~Si-OC 2 H 5 . Hydrolysis of these groups and polycondensation of the resulting silanols ~Si-OH at low temperatures occur very slowly, aided by the content in the composition of the solvent. For example, the composition is at a temperature of 60°C has a time of fluidity loss order 9-18 o'clock At lower formation temperatures of this period will be much longer (up to several days), that will cause care composition from plugging. In addition, cured working solution (usually, the composition is diluted with water 2-3 times immediately before injection into the well) has insufficient strength characteristics, which is of special importance in the context of high depressions on the formation. Thus, having advantages for injection into high-temperature reservoirs, especially low permeability, the composition is not suitable or unsuitable for use at low formation temperatures, especially in the presence of inter-layer flows and high reservoir permeability, fractured and vuggy fractured reservoirs. For these conditions, the time loss of fluidity injected into the layer of composition must be determined by more active processes of hydrolysis and polycondensation. In order for these reactions proceeded more quickly, it is necessary that the composition contained some amount of hydrolyzable groups are more active in comparison with ethoxyline groups. Closest to the proposed invention is a cement composition comprising the esterification product of hydrolytic charcterised distillation of astakov production of organosilicon monomers (methylchlorosilanes, ethylchloride or phenyltrichlorosilane) followed by treatment of the acid with the alcohol and removing hydrolyzable chlorine (RU # 2068848, class C 07 F 7/08, publ. 10.11.1996). Specified the grouting composition is characterized by a content of active chlorine ion from 4 to 8 wt.%. The objective of the invention is to provide a cement composition with controlled gelation time, ensuring its application in low-temperature collectors, including high permeability. In addition, in the invention include providing a composition with a long shelf life, ability of its manufacture in the factory. The invention consists in that the grouting composition comprising the esterification product of hydrolytic bottoms of phenyltrichlorosilane aqueous solution of alcohol according to the invention as specified product contains a hydrolytic product of esterification 100 parts by weight of chlorine-containing bottoms of phenyltrichlorosilane 10-32,8 parts by weight of 90-93%aqueous solution of the alcohol in the presence of 10-40 parts by weight of ethyl ester of orthosilicic acid and optionally 15-35 parts by weight of chlorine-containing bottoms of phenyltrichlorosilane when the total content of the last and the specified product 133,2-161,6 parts by weight additionally, the composition may optionally contain up to 16.8 parts by weight of the polar solvent. The composition of the bottoms is not constant, in particular mass fraction FTHS in them ranges from 10 to 40%, mass fraction of organically bound chlorine is also changing. For the esterification and partial hydrolysis of the chlorine-containing bottoms FTHS take strictly equivalent amount of water-alcohol mixture with a volume fraction of alcohol 90-93%, to completely expose the esterification of chlorine ions, which corresponds to the content 10-32,8 parts by weight of ethyl alcohol. In this case the result is oligoetoxichlorsiloxane with generousity properties. To improve properties of the resulting cement composition in the reaction mass during the process of obtaining oligoetoxichlorsiloxane entered ethyl ester of orthosilicic acid, while the grouting fluid is more homogeneous, forming when melirovanie elastic homogeneous gel, turning into a solid form. The optimal amount of ethyl ester of orthosilicic acid is 10-40 parts by weight Without the introduction of grouting fluid forms krupinsky, inhomogeneous gel. The content of the ethyl ester of orthosilicic acid is more than 40 parts by weight does not change properties. The number of additionally introduced into oligodeoxynucleotides chlorine-containing bottoms FTHS is determined by the mass fraction of chlorine-ion in the finished product, which should be in the range of 4.0 to 8.0%, and this interval is provided by the introduction of 15-35 parts of chlorine-containing bottoms FTHS. The proposed grouting composition is a homogeneous movable fluid is dark in color with a viscosity of no more than 30 seconds by the viscometer VZ-246 and the gelation time 5-45 min at 20±5°C. Introduction in the grouting composition of the polar solvents can increase the gelation time to 120-360 min, which may be necessary to meet the specific requirements of certain oil wells. However, with the increasing number of solvents more than 16.8 parts by weight decreases the viscosity of the cement composition and is the excessive increase in the time of gelation, as well as deteriorates the storage stability. Examples of specific performance: Used in the experiments reagents: ethyl esters articlenews acid: tetraethoxysilane (TU 6-00-576445014-90), ethyl silicate-32 (TU 6-02-895-86), ethyl silicate-40 (GOST 26371-84), product 119-296 (TU 6-00-05763441-45-92); - polar solvents: isopropyl alcohol, ethylene glycol, triethylene glycol; afuraldehyde fraction; - chlorine-containing distillation residues from the production of phenyltrichlorosilane (FTHS). Example 1 Into the reaction flask with stirrer, thermometer, refrigerator and addition funnel download 100 parts by weight of chlorine-containing bottoms of phenyltrichlorosilane, 23,17 parts by weight of the product 119-296, a few drops of antifoam (to prevent subsequent foaming), stirred for 30 min and a dropping funnel loads of water-alcohol mixture in an amount equal to 27.4 parts by weight at the temperature of the reaction mixture to 20-25°C. Upon completion of the esterification mass is stirred for 30 minutes and spend the desorption of hydrogen chloride at 130-140°C until the mass fraction of residual chlorine of 0.2-2%. After desorption of hydrogen chloride and cooling the reaction mixture below 60°C are loaded into the mass of chlorine-containing distillation residues FTHS in the number 27,17 parts by weight to achieve mass fraction of CL - ion in the product 4,0-8,0%. The resulting composition is a homogeneous thin liquid. Variants of cement composition and test results are presented in the table. The gelation time determined by adding water to the resulting composition at a ratio of 1:2. The gelation time (curing) of the composition is considered to be the time since the start of incubation until the meniscus weight when tilted closed tubes (or flask) at 45° is not shifted. Water capacity of the composition is determined by comparing the performance of the permeability of water through the model sand core to saturation of its investigational compound and after saturation and temperature during the day at 25°C. Examples of the composition of the other components of the test conditions and the results tested by the above methods are shown in table 1. In all cases there is a decrease in permeability model cores more than 97%, which confirms the high gelling properties of the investigated compounds. To determine the duration of storage of the prepared compositions were left in sealed flasks at room temperature and every 3 months made the study of their properties by the following methods. After 12 months of storage divergence indicators compared with a freshly prepared compounds did not exceed 5%, which is within the confidence interval of the analyzed parameters, and confirms their high consumer properties after long-term storage. Enter hydrolyzable chlorine and solvents in the inventive composition allows to maintain a positive prototype properties (high-plugging ability, controllability the curing time, the possibility of prefabrication, and others), to achieve the optimal time of fluidity loss in the low-and high-permeability reservoirs, as well as be used to eliminate areas of acquisitions and rudoproyavlenii. Table no experience Getting oligoetoxichlorsiloxane getting the finished product quantity of the finished product Mac. the proportion of CL - , % gelation Time, at 25±5°C min Distillation leave FTHS Ethyl ester of orthosilicic acid VSS Oligoadenylate Distillation leave FTHS Solvent Parts Mac. the proportion of CL - , % name Parts by weight Parts by weight Parts by weight of a Mac. the proportion of CL - , % Parts name Parts 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 100 28,6 Product 119-296 23,17 27,4 121,7 1,24 27,17 - - 148,57 7,09 15 2 100 27,0 - 13,17 24,67 112,1 0,96 30,0 - - 141,7 7,17 25 3 100 28,6 - 16,39 26,9 115,5 1,01 20,19 - - 134,9 4,55 20 4 100 24,13 - 35.5 24,1 134,7 1,37 23,88 TAG 10,56 168,9 4,1 150 5 100 27,63 - 14,66 25,9 114,2 1,71 19,3 TAG 6,1 139,3 5,2 90 6 100 29,58 ETS-40 37,35 29,6 136,9 0,71 25,4 IPS 14,2 175,8 6,81 45 7 100 29,58 - 19,3 30,3 118,7 1,61 26,92 IPS 4,81 150,1 5,85 40 8 100 25,83 - 25,46 27,3 124,9 1,31 22,96 EAT 7,64 155,21 6,45 8 9 100 26,11 - 25,81 26,3 125,31 1,17 28,6 EAT 6,6 160,11 3,85 5 10 100 27,6 ETS-32 32,8 27,8 132,31 1,2 28.4 IPS 16,8 176,7 7,3 360 1 2 3 4 5 6 7 8 9 10 11 12 13 14 11 100 27,6 - 14,7 28,3 114,1 0,98 21, IPS 5,2 140,2 6,9 30 12 100 27,56 TEOS 18,4 26,4 117,9 0,93 19,9 EH 8,1 145,3 6,1 18 13 100 27,56 - 23,8 27,1 123,3 1,1 21,3 EH 18,3 162,1 6,7 Not helium 14 100 31,0 Product 119-296 33,3 32,0 131,41 1,63 24,7 EH 15,3 170,11 4,8 Separates water 15 100 28,6 - 18,7 30,0 117,8 1,98 22,3 Acetone 15,8 155,9 5.8 Not helium 16 100 27,6 - 22,4 28,1 121,6 0,83 27,4 - 7,4 156,4 6,1 120 17 100 27,6 - 10,0 27,3 109,3 0,87 26,8 - - 135,3 5,9 25 18 100 28,6 - 40,0 28,7 137,0 0,89 25,9 - - 161,3 4,8   Refer: FDS - phenyltrichlorosilane TAG - triethylene glycol ETS - ethyl silicate EG - ethylene glycol TEOS - tetraethoxysilane IPA - isopropyl alcohol WBU - water-alcohol mixture AAF - afuraldehyde fraction 1. The grouting composition comprising the esterification product of hydrolytic chlorine-containing bottoms of phenyltrichlorosilane aqueous solution of alcohol, characterized in that it contains as the specified product hydrolytic product of esterification 100 parts by weight of chlorine-containing bottoms of phenyltrichlorosilane 10-32,8 mass. including 90-93%aqueous solution of the alcohol in the presence of 10-40 parts by weight of ethyl ester of orthosilicic acid and optionally 15-35 parts by weight of chlorine-containing bottoms of phenyltrichlorosilane when the total content of the last and the specified product 133,2-161,6 parts by weight of Campanini composition according to claim 1, characterized in that it additionally contains up to 16.8 parts by weight of the polar solvent.