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Liquid formula used for in-depth acidification of high temperature carbonate rock

A carbonate rock, deep acidification technology, applied in the direction of chemical instruments and methods, drilling compositions, etc., can solve the problems that the hydrolysis rate cannot reach 100%, the generation of precipitation, the blockage of pipelines, etc.

Active Publication Date: 2012-04-04
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The self-acids in the above-mentioned patents mainly use esters to hydrolyze to produce organic acids. The types of organic acids are formic acid, acetic acid, propionic acid, lactic acid, etc. With the increase of the C chain, the greater the molecular weight, the [H + ] concentration is lower, so the [H + ] is the maximum, according to data, the maximum amount of formic acid that can be used in field applications cannot exceed 10%, which is equivalent to [H + ]=2.2mol / L, and if the organic acid is produced by hydrolysis of the ester, it is inferred from the dissociation constant that the hydrolysis rate cannot reach 100%
Not only that, the reaction between organic acid and calcium carbonate is very easy to produce organic calcium precipitation, which will cause precipitation and block the pipeline in the case of blowout, so it is unrealistic to use organic ester hydrolysis to achieve deep acidification of high-temperature deep wells

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Prepare an aqueous solution containing 10% methyl formate + 0.5% fluorocarbon surfactant, add excess marble stones, put them together in a container that can be sealed for temperature rise and pressure, raise the temperature to 60°C, take a sample after reacting for 1 hour, and filter the liquid , weighed dry, and calculated the released [H + ]=1.07mol / L. Repeat the above formula loading, the released [H + ]=1.32mol / L, the [H released after reaction 3h + ]=1.46mol / L, the [H released after reaction 4h + ]=1.48mol / L. After three hours, the hydrolysis of methyl formate basically reached equilibrium, and no longer released H + .

Embodiment 2

[0017] Prepare an aqueous solution containing 10% formic acid + 10% chloroacetic acid + 0.3% fluorocarbon surfactant, add excess marble stones, put them together in a container that can be sealed for temperature rise and pressure, raise the temperature to 90°C, and take a sample after reacting for 1 hour Filter the liquid, weigh it dry, and calculate the released [H + ]=2.6mol / L. Repeat the above formula loading, the released [H + ]=2.82mol / L, the [H released after reaction 3h + ]=3.0mol / L, the released [H + ]=3.2mol / L, continue to react its release hydrogen ion concentration and no longer increase.

Embodiment 3

[0019] Prepare an aqueous solution containing 16% ammonium chloride + 13.5% formaldehyde + 20% ethyl lactate + 1% betaine surfactant, add excess marble stones, and put them together in a closed container that can be heated and pressurized. Introduce high-pressure nitrogen gas to raise the pressure in the container to 2MPa, then raise the temperature of the container to 150°C, and keep the temperature and pressure constant. The [H released after 1 h of reaction was measured + ]=1.9mol / L, [H released after 2h + ]=2.56mol / L, [H released after 3h + ]=3.1mol / L, [H released after 4h + ]=3.2mol / L, continue to react its release hydrogen ion concentration and no longer increase. Its formula is as follows:

[0020] 4NH 4 Cl+6CH 2 O→N 4 (CH 2 ) 6 +4HCl+6H 2 o

[0021] CH 3 CH(OH)COOCH 2 CH 3 +H 2 O→CH 3 CH(OH)COOH+CH 3 CH 2 Oh

[0022] 2HCl+CaCO 3 →CaCl 2 +CO 2 +H 2 o

[0023] 2CH 3 CH(OH)COOH+CaCO 3 →(CH 3 CH(OH)COO) 2 Ca+CO 2 +H 2 o

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Abstract

The invention relates to a liquid formula used for in-depth acidification of high temperature carbonate rock. The liquid formula is applicable at a temperature of 60 to 150 DEG C and comprises, on the basis of mass percentage, 10 to 50% of organic ester, 0 to 50% of halogen acid series, 0 to 45% of ammonium halide, 0 to 50% of formaldehyde or a mixture thereof and 0.1 to 5% of a surfactant. According to the invention, through adjusting of release of H<+> at 2.2 to 4 mol / L and generation of H<+> through hydrolysis at a temperature of 60 to 150 DEG C, the release speed of an acid solution is controlled to be in a range of 0.5 h to 6 h, which enables the problem of the reaction rate of a high temperature carbonate rock storage layer to be overcome and in-depth acidification to be realized; different addition amount of the liquid formula and different processes can be employed according to different formation conditions, and the liquid formula can be used for acidification, pickling and in-depth acid fracturing of carbonate rock and low molecular fracturing fluid acidic gel breakers; components in the liquid formula can be used individually according to different demands.

Description

technical field [0001] The invention relates to a formula suitable for deep acidification of high-temperature (60-150 DEG C) carbonate rock reservoirs. Background technique [0002] Acidizing or acid fracturing is the main production stimulation measure for carbonate rock reservoirs. The method is to inject acid liquid into the formation to dissolve the mineral composition of the reservoir rock and to block the reservoir during drilling, completion, workover and oil production operations. Substances can improve and enhance the permeability of reservoirs, thereby increasing the productivity of oil and gas wells. [0003] The acidizing of high-temperature deep wells and sulfur-containing gas wells mainly faces four problems: first, the reaction speed of carbonate rocks is fast at high temperatures, which is difficult to control; second, the acid liquid at high temperatures corrodes the tubing severely; The frictional resistance along the process is high, the construction pump...

Claims

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Application Information

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IPC IPC(8): C09K8/74
Inventor 刘友权张倩王小红石晓松张永国陈鹏飞王川
Owner PETROCHINA CO LTD
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