阅读说明：本技术 一种造纸废液凝胶调剖堵水剂及其制备方法 (Papermaking waste liquid gel profile control water shutoff agent and preparation method thereof ) 是由 齐宁 王雪涛 任兴华 韩子昭 蒋平 何龙 张合文 于 2020-05-25 设计创作，主要内容包括：一种造纸废液凝胶调剖堵水剂,包括造纸废液、水溶性酚醛树脂、腈类聚合物：其中所述水溶性酚醛树脂的用量为造纸废液质量的6-10wt％,所述腈类聚合物的用量为造纸废液质量的0.1-0.75wt％；其中所述造纸废液中含有纤维素和/或碱木素,其中纤维素和/或碱木素的总含量为5-10wt％。所述调剖堵水剂适用温度高、成胶时间短、成胶强度大,具有良好的成胶性能,能够实现快速、有效封堵,具有良好的成胶性能,具有良好的耐高矿化度性能；调剖堵水剂在近中性、碱性条件下成胶,且成胶后具有良好的耐酸碱性能。(A papermaking waste liquid gel profile control water shutoff agent comprises papermaking waste liquid, water-soluble phenolic resin and nitrile polymer: wherein the dosage of the water-soluble phenolic resin is 6-10 wt% of the mass of the paper-making waste liquid, and the dosage of the nitrile polymer is 0.1-0.75 wt% of the mass of the paper-making waste liquid; wherein the papermaking waste liquid contains cellulose and/or alkali lignin, wherein the total content of the cellulose and/or alkali lignin is 5-10 wt%. The profile control water shutoff agent has high applicable temperature, short gelling time, high gelling strength, good gelling performance, can realize quick and effective plugging, and has good gelling performance and good high mineralization resistance; the profile control water shutoff agent is gelled under the conditions of near neutrality and alkalinity, and the gelled agent has good acid and alkali resistance.)

1. A papermaking waste liquid gel profile control water shutoff agent comprises papermaking waste liquid, water-soluble phenolic resin and nitrile polymer: wherein the dosage of the water-soluble phenolic resin is 6-10 wt% of the mass of the paper-making waste liquid, and the dosage of the nitrile polymer is 0.1-0.75 wt% of the mass of the paper-making waste liquid; wherein the papermaking waste liquid contains cellulose and/or alkali lignin, wherein the total content of the cellulose and/or alkali lignin is 5-10 wt%.

2. The water plugging agent according to claim 1, wherein the water-soluble phenol resin and the nitrile polymer are used by being previously dissolved in a solvent, wherein the concentration of the water-soluble phenol resin is 5 to 12 wt%, and the concentration of the nitrile polymer is 0.5 to 2 wt%; the solvent is one or more of water, ethanol, methanol and propanol; the nitrile polymer is one or more of soluble nitrile bond containing polymers, preferably partially hydrolyzed polyacrylonitrile.

3. The water shutoff agent according to claim 1, wherein the paper making waste liquid comprises solid pulp and paper making waste liquid, the solid pulp is subjected to infrared spectroscopy to determine the content of alkali lignin and/or lignin, and the paper making waste liquid is subjected to ultraviolet spectroscopy to determine the content of alkali lignin and/or lignin.

4. The plugging agent of claim 1, wherein the papermaking waste liquid gel profile control plugging agent comprises 8-10 wt% of water-soluble phenolic resin and 0.4-0.7 wt% of nitrile polymer based on the mass of the papermaking waste liquid.

5. The plugging agent of claim 1, wherein the working temperature of the papermaking waste liquid gel profile control plugging agent is 20-170 ℃, the gelling time is 3.5-12h, the gelling time is controllable, and the strength of the generated gel is 0.02-0.07 MPa.

6. The plugging agent according to claim 1, wherein preferably, the papermaking waste liquid gel profile control plugging agent has gelling time of 3.5-12h and gelling strength of 0.039-0.051MPa within the temperature range of 100-150 ℃; more preferably, the gelling time of the papermaking waste liquid gel profile control water shutoff agent is 3.5h and the gelling strength is 0.051MPa at the temperature of 150 ℃.

7. The plugging agent according to claim 1, wherein the papermaking waste liquid gel profile control plugging agent can be used in water with NaCl concentration of 0-200000mg/L and pH of 7-14.

8. The water shutoff agent according to claim 1, wherein the concentration of alkali lignin and/or lignin is increased by subjecting the paper making waste liquid to distillation under reduced pressure, and the pH value is adjusted to 10 to 14.

9. The method for preparing the papermaking waste liquor gel profile control water shutoff agent according to any one of claims 1 to 8, comprising the following steps:

(1) according to the composition of the profile control water shutoff agent, weighing corresponding mass of water-soluble phenolic resin, nitrile polymer and papermaking waste liquor containing alkali lignin, and dissolving the water-soluble phenolic resin and the nitrile polymer in a solvent.

(2) Under the condition of continuous stirring, respectively and sequentially adding the water-soluble phenolic resin solution and the nitrile polymer solution into a beaker filled with the papermaking waste liquid, and stirring the mixture until the mixture is uniform.

(3) And (3) filling the profile control water plugging agent solution obtained in the step (2) into a container, sealing, naturally cooling the container, placing the container into a high-temperature tank, placing the container into an electric heating air blast drying box, and reacting to form gel at 50-150 ℃ to obtain the papermaking waste liquor gel profile control water plugging agent.

10. Use of the profile control water shutoff agent of any of claims 1-8 in near well shutoff and deep shutoff of oil and gas wells by varying the concentrations of the crosslinking agent and the toughening agent to extend gel formation time.

Technical Field

The invention relates to a papermaking waste liquid gel profile control water shutoff agent and a preparation method thereof, belonging to the technical field of oil and gas field profile control water shutoff agents.

Background

The profile control water shutoff is a water control and oil stabilization measure commonly used in water-drive oil fields, and the major key of the success of the profile control water shutoff lies in the performance of the profile control water shutoff agent, in recent years, along with the continuous deepening of oil field development, the problems of the profile control water shutoff are increased, wherein the profile control water shutoff is particularly prominent in the profile control water shutoff of the west depth and the thick oil, the oil reservoir is deep, high in temperature, large in mineralization degree and low in crude oil fluidity, and the existing profile control water shutoff agent has the mineralization degree of 5 × 10 for the temperature of less than 100 ℃ and the mineralization degree of 5 8910⁴The plugging layer below mg/L has good effect, the strength of the profile control plugging agent exceeding the limit is greatly reduced, and even the gel cannot be formed, so that the profile control plugging agent is required to be resistant to the influence of high temperature and high salinity; in addition, in order to effectively control water, a large-dose and multi-section plug plugging adjusting mode is mostly adopted in the later stage of water-driven oil field development, but large-dose plugging adjusting also brings huge cost pressure to oil field development. Therefore, it is imperative to develop a profile control water shutoff agent with low cost, high temperature resistance and high mineralization degree.

The papermaking waste liquid contains alkali lignin or lignin, which can react with the cross-linking agent water-soluble phenolic resin under proper external conditions to generate gel with certain strength. The alkali lignin or lignin contains groups such as p-hydroxyphenyl, syringaldehyde phenyl, Shu Chua lignan group, carboxymethyl and the like, and the groups have certain activity, and can generate crosslinking reaction with a crosslinking agent water-soluble phenolic resin in the reaction process to generate gel with a space network structure, so that the gel has higher strength. Therefore, the papermaking waste liquid is used as a main agent, the water-soluble phenolic resin and the toughening agent are combined, and a papermaking waste liquid gel system is formed through a cross-linking reaction, so that the plugging construction cost can be greatly reduced, and the system has a good plugging effect.

Disclosure of Invention

The invention mainly adopts water-soluble phenolic resin as a cross-linking agent according to the molecular structure characteristics of alkali lignin or lignin in the papermaking waste liquid, and can perform cross-linking reaction with active groups such as p-hydroxyphenyl, aldehyde group, carboxymethyl and the like on the alkali lignin or lignin structure in the papermaking waste liquid to form a space network structure. The nitrile polymer as the toughening agent can improve the gel strength and stability of the system through the twisting and winding of a linear molecular chain of the nitrile polymer. The papermaking waste liquid gel profile control water shutoff agent has good gelling strength and stability.

The water-soluble phenolic resin can be subjected to a crosslinking reaction with alkali lignin or lignin compounds in the papermaking waste liquid within a proper temperature and pH value range to form gel, so that the gel strength and stability of the papermaking waste liquid gel profile control water plugging agent are obviously enhanced.

The invention provides a papermaking waste liquid gel profile control water shutoff agent, which comprises the following components in parts by weight: wherein the dosage of the water-soluble phenolic resin is 6-10 wt% of the mass of the paper-making waste liquid, and the dosage of the nitrile polymer is 0.1-0.75 wt% of the mass of the paper-making waste liquid; wherein the papermaking waste liquid contains cellulose and/or alkali lignin, and the total content of the cellulose and/or alkali lignin is 5-10 wt%.

The water-soluble phenolic resin and the nitrile polymer are dissolved in a solvent in advance for use, wherein the concentration of the water-soluble phenolic resin solution is 5-12 wt%, and the concentration of the nitrile polymer solution is 0.5-2 wt%; the solvent is one or more of water, ethanol, methanol and propanol.

The papermaking waste liquid comprises solid paper pulp and/or papermaking waste liquid, wherein the solid paper pulp adopts an infrared spectrum experiment to determine the content of alkali lignin and/or lignin, and the papermaking waste liquid adopts an ultraviolet spectrum experiment to determine the content of alkali lignin and/or lignin.

Preferably, the content of the water-soluble phenolic resin is 8-10 wt% of the mass of the paper-making waste liquid, and the content of the nitrile polymer is 0.4-0.7 wt% of the mass of the paper-making waste liquid.

The working temperature of the papermaking waste liquid gel profile control water shutoff agent is 20-170 ℃, the gelling time is 3.5-12h, and the strength of the generated gel measured by a breakthrough vacuum degree method is 0.02-0.07 MPa.

Preferably, the gel profile control water shutoff agent for the papermaking waste liquid gel is prepared in a gelling time of 3.5-12h and a gelling strength of 0.039-0.051MPa within a temperature range of 100-150 ℃.

More preferably, the gelling time of the papermaking waste liquid gel profile control water shutoff agent is 3.5h and the gelling strength is 0.051MPa at the temperature of 150 ℃.

The papermaking waste liquid gel profile control water shutoff agent can be used in water with NaCl concentration of 0-200000mg/L and pH of 7-14.

Preferably, the concentration of the alkali lignin and/or lignin is increased by the reduced pressure distillation treatment of the papermaking waste liquid, and the pH value of the concentrated papermaking waste liquid is adjusted to 10-14.

The nitrile polymer is one or more of soluble nitrile bond containing polymers, preferably partially hydrolyzed polyacrylonitrile.

The preparation method of the papermaking waste liquid gel profile control water shutoff agent comprises the following steps:

(1) weighing water-soluble phenolic resin, nitrile polymer and papermaking waste liquid containing alkali lignin according to the composition of the profile control water plugging agent, and dissolving the water-soluble phenolic resin and the nitrile polymer in a solvent;

(2) under the condition of continuous stirring, respectively and sequentially adding the water-soluble phenolic resin solution and the nitrile polymer solution into a beaker filled with the papermaking waste liquid, and stirring the mixture until the mixture is uniform.

(3) And (3) filling the profile control water plugging agent solution obtained in the step (2) into a container, sealing, naturally cooling, placing the container into a high-temperature tank, placing the tank into a drying box, and reacting to form gel at 50-150 ℃ to obtain the papermaking waste liquid gel profile control water plugging agent.

And (3) stirring for 5-60min in the step (2).

The profile control water shutoff agent is applied to near-well plugging and deep plugging of oil and gas wells. The deep plugging is realized by changing the concentrations of the cross-linking agent and the toughening agent to prolong the gelling time. When the concentration of other components is unchanged, the lower the concentration of the crosslinking agent and/or the toughening agent is, the longer the gelling time is.

The invention has the beneficial effects that:

(1) the profile control water shutoff agent disclosed by the invention is high in applicable temperature, short in gelling time, high in gelling strength, good in gelling performance, capable of realizing rapid and effective plugging, and good in gelling performance.

(2) The profile control water shutoff agent can realize quick and effective shutoff in a high-salinity reservoir and has good high-salinity resistance.

(3) The profile control water shutoff agent is gelled under the conditions of near neutrality and alkalinity, and the gelled agent has good acid and alkali resistance.

(4) The papermaking waste liquid gel profile control water shutoff agent has low cost and simple preparation, and is suitable for the profile control water shutoff operation of high-temperature and high-salinity oil reservoirs.

Drawings

FIG. 1 is a physical diagram of a gel profile control water shutoff agent of the papermaking waste liquid in example 1.

Detailed Description

The formulations and their properties of the present invention are illustrated in detail below by way of examples, but are not limited thereto.

The main medicines are as follows: the paper mill waste liquid, the water-soluble phenolic resin (the effective solid content is 35 percent), the nitrile polymer, NaOH and NaCl are all chemical reagents of the national drug group, and the analysis is pure.

The main apparatus is as follows: JJ-1 power-increasing electric stirrer, pH meter (thunder magnetic PHS-3C), alcohol blast lamp, electronic balance (BSA423S), electrothermal blowing dry box, high-temperature tank, vacuum pump, etc.

Evaluation of gelling performance of papermaking waste liquid gel profile control water shutoff agent

And (3) determining the gelling time: periodically taking out the ampoule bottle and horizontally placing, observing an angle formed between the upper surface of the gel and the bottom surface of the ampoule bottle, judging that the gel is formed and recording the gel forming time if the angle is more than 45 degrees, and otherwise, continuing to react until the gel is formed.

Testing the gel forming strength: evaluating the strength of the gel by adopting a GSC strength code method (see table 1), and if the strength is higher than G level, testing the breakthrough pressure by adopting a breakthrough vacuum degree method to obtain the gel strength; if it is less than the G level, only the intensity code is recorded.

TABLE 1

Evaluation of temperature resistance of papermaking waste liquid gel profile control water shutoff agent

The gel of the profile control water shutoff agent is respectively put into 6 ampoule bottles and sealed, the temperature is gradually raised from 100 ℃, and whether the gel state is intact or not and whether dehydration or liquefaction exists or not is observed.