CN115725289B - Phenolized modified lignin-based channeling sealing agent and preparation method and application thereof - Google Patents
Phenolized modified lignin-based channeling sealing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a phenolized modified lignin-based channeling sealing agent, and a preparation method and application thereof. The channeling sealing agent is prepared from the following raw materials: phenolated lignin, thickeners, cross-linking agents, modifiers, stabilizers, and formulation water. The preparation method of the channeling sealing agent comprises the following steps: adding a thickening agent into the prepared water for full dissolution, adding phenolized lignin, a cross-linking agent, an improver and a stabilizer, adjusting the pH value, and uniformly stirring to obtain the channeling sealing agent. The channeling sealing agent expands the temperature application range, has higher strength, has the characteristics of large blocking strength, wide application range, high blocking efficiency and the like, can effectively block a steam channeling channel for a long time, and realizes the efficient development of heavy oil reservoirs. The channeling sealing agent disclosed by the invention also effectively reduces the concentration of the main agent and the cross-linking agent, reduces the production cost of the channeling sealing agent, meets the requirements on the performance and the economy of site construction, and has higher practicability.
Description
Technical Field
The invention relates to the technical field of oilfield chemicals, in particular to a phenolized modified lignin-based channeling sealing agent, a preparation method and application thereof.
Background
At present, thermal recovery technology using steam huff and puff, steam flooding and the like as main recovery modes is a main mode adopted in the development of thick oil in countries around the world. In the later period of thick oil development, the problems of low injection ratio, low formation pressure, serious steam channeling, sand production, flooding of side water, high stable yield and the like occur due to the limitations of the reasons such as non-development of stratum interlayers, the difference of permeability between strata, development conditions and the like.
Various methods for thick oil seal steam channeling and side water invasion inhibition exist, but the defects such as poor blocking effect of mechanical blocking in the longitudinal direction are common; the cement or solid slurry is used for plugging the underground high-permeability layer, and the biggest problem is that the oil-containing production layer is also plugged. The method for controlling the profile and injecting the steam by using the chemical plugging agent is also an effective method for controlling the steam channeling, and at present, the channeling sealing agent mainly comprises oil-in-water emulsion, steam foam, inorganic particles, high-temperature gel and the like. The foam injection site construction process is complex, and inorganic particles tend to stay in near-wellbore areas. Therefore, the most widely used high temperature gel is the one, and in recent years, haliberton and the like develop a high temperature gel which takes acrylamide-tert-butyl acrylate copolymer as a high polymer and polyethyleneimine as a cross-linking agent and can resist the temperature of 200 ℃, but the high temperature gel is not applied at home.
Lignin is a three-dimensional network structure formed by combining phenylpropyl with ether (C-O-C) or carbon-carbon bond (C-C) to form hetero-branched chains, and the lignin is second only to cellulose in the natural world and is a second largest natural organic matter. The industrial lignin has rich sources and low cost, and can be used as a raw material for producing oilfield chemicals. Along with the rising price of petrochemical raw materials and the increasing environmental protection requirement, green chemicals using low-cost natural renewable resources such as lignin and the like as raw materials have become an international hot spot research and development direction.
The channeling sealing agent is prepared by using lignin, so that waste can be changed into valuable, and the production cost is low. However, the connection mode between lignin structural bodies is mainly ether bond and carbon-carbon bond, and the two bond molecules have small polarity, high bond energy and difficult reaction, and have high methoxy content, low hydroxyl content, large steric hindrance on benzene ring and obvious insufficient reaction activity. For the problem of few lignin crosslinking sites, the problem of few lignin crosslinking sites is generally solved by increasing the addition amount in the prior art, so that the dosage of lignin and crosslinking agent in the prior system is higher.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a phenolized modified lignin-based channeling sealing agent, and a preparation method and application thereof. The viscosity of the channeling sealing agent is 9.3-21.6 mPa.s at normal temperature (25 ℃), and the channeling sealing agent has good pumpability; the adhesive can be controllably formed into adhesive (1.5-120 h) within a wider temperature range (100-300 ℃), and the strength is between 0.071 and 0.086MPa; and the gel is not broken at the high temperature of 300 ℃ for 60 days, the dehydration rate is less than 4.9%, the plugging rate is higher than 99.06%, the steam channeling channel is effectively plugged for a long time, and the high-efficiency development of the heavy oil reservoir is realized. The channeling sealing agent expands the temperature application range, has higher strength, has the characteristics of large blocking strength, wide application range, high blocking efficiency and the like, effectively reduces the concentration of the main agent and the cross-linking agent, reduces the production cost of the channeling sealing agent, meets the requirements of site construction performance and economy, and has higher practicability.
The invention aims to provide a phenolized modified lignin-based channeling sealing agent, which is prepared from the following raw materials:
phenolated lignin, thickener, cross-linker, modifier, stabilizer and formulation water;
based on the total weight of the raw materials as 100 percent,
the content of phenolized lignin is 1.5-3.5wt%;
the content of the thickener is 0.001-0.15wt%;
the content of the cross-linking agent is 0.02-2.5wt%;
the content of the modifier is 0.01-0.05wt%;
the content of the stabilizer is 0.001-0.05wt%.
Preferably, in order to further obtain better effects, in particular, the channeling sealing agent can realize controllable crosslinking at a higher gel forming temperature, and the gel strength is better,
based on the total weight of the raw materials as 100 percent,
the phenolated lignin content is 2-3wt%;
the content of the thickener is 0.05-0.1wt%;
the content of the cross-linking agent is 0.8-2wt%;
the content of the modifier is 0.02-0.04wt%;
the content of the stabilizer is 0.01-0.03wt%.
The channeling sealing agent is preferably prepared with water in an amount such that the above components are within the ranges. The skilled person can determine this according to the actual situation.
Preferably, the method comprises the steps of,
the preparation method of the phenolized lignin comprises the following steps:
adding lignin and phenol into a base catalyst solution, carrying out contact reaction under heating and reflux conditions to obtain a solution containing phenolated lignin, cooling to room temperature, adjusting the pH value to be acidic, and purifying to obtain the phenolated lignin.
In the present invention, the lignin, phenol and base catalyst are all commercially available.
Preferably, the method comprises the steps of,
the lignin is at least one selected from alkali lignin, enzymolysis lignin, chlorination lignin, steam explosion lignin and sulfur lignin; preferably at least one of alkali lignin and enzymatic lignin; more preferably, the lignin is present in the lignin in an effective amount of from 80 to 99.9wt%; and/or the number of the groups of groups,
the phenol is selected from at least one of phenol, hydroquinone, resorcinol and catechol; and/or the number of the groups of groups,
the alkali catalyst is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
Preferably, the method comprises the steps of,
in the reaction system of the contact reaction,
the concentration of the lignin is 10-15wt%;
the mass ratio of the phenol to the lignin is 0.2-0.4:1;
the mass ratio of the alkali catalyst to the lignin is 0.12-0.3:1;
heating at 70-85deg.C for 0.5-2 hr;
in the present invention, the conditions for the contact reaction are not particularly limited, and the phenolization modification of lignin may be achieved. The inventor finds that better effect can be obtained when the phenolized lignin obtained under the phenolization condition that the temperature is 70-85 ℃ and the time is 0.5-2h is used in the high-temperature channeling sealing agent in the research;
the pH value is adjusted to 2-3; the method of adjusting the pH is a method commonly used in the art, and preferably, the pH adjustment is performed by adding an acidic substance, which may be at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid.
The purification may be carried out by a purification method conventional in the art, for example, in the present invention, the mixture solution obtained after the reaction is centrifuged, followed by repeated washing and finally vacuum drying.
The inventor of the invention unexpectedly discovers in the research that the alkaline phenolization modification is carried out on lignin to obtain phenolized lignin, so that the phenolic hydroxyl content of the lignin is improved, the crosslinking site of the lignin is increased, the crosslinking activity of the lignin is improved, and finally, the performance of the channeling sealing agent is improved. In the system, the rigid molecular structure of the phenolized lignin and the flexible molecular structure of the amide thickener polymer are complementary to each other to form an interpenetrating network gel structure; the high-temperature channeling sealing agent is matched with other components for use, can be controlled to be gel (1.5-120 h) within a wider oil reservoir temperature (100-300 ℃) range, does not break gel within 60 days at 300 ℃, has a dehydration rate of less than 4.9%, expands the temperature use range and has higher strength; the plugging agent has the characteristics of low initial viscosity, high plugging strength, wide application range, high plugging efficiency and the like, effectively reduces the production cost of the high-temperature channeling blocking agent, meets the requirements of site construction on performance and economy, and has higher practicability.
Preferably, the method comprises the steps of,
the thickener is an amide thickener; preferably at least one selected from Acrylamide (AM)/2-acrylamide-2-methylpropanesulfonic Acid (AMPS) copolymers; specifically at least one of AM/AMPS copolymers with different AM/AMPS proportions or different molecular weights; the molecular weight of the thickener is 500-3000 ten thousand; preferably, the molecular weight of the thickener is 1000 to 2000 ten thousand; and/or the number of the groups of groups,
the cross-linking agent is at least one of water-soluble phenolic resin prepared by taking phenol, homologs thereof and aldehydes as raw materials, and the effective content is preferably more than 38 weight percent.
Preferably, the method comprises the steps of,
the modifier is selected from Mn 2+ 、Ti 4+ At least one of the soluble salts of (a); more preferably, the modifier is selected from at least one of titanium sulfate, titanium chloride, manganese sulfate or manganese chloride; and/or the number of the groups of groups,
the stabilizer is at least one selected from sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, isoascorbic acid or thiourea; and/or the number of the groups of groups,
the water to be prepared is not particularly limited, and may be river, lake, sea water, groundwater, artificial water, oilfield produced water, etc., preferably water having a mineralization degree of less than 100000mg/L, more preferably water having a mineralization degree of less than 50000 mg/L.
It is a second object of the present invention to provide a method for preparing a phenolized modified lignin-based channeling blocking agent according to one of the objects of the present invention, the method comprising the steps of:
adding a thickening agent into the prepared water for full dissolution, adding the phenolized lignin, a cross-linking agent, an improver and a stabilizer, adjusting the pH value, and uniformly stirring to obtain the phenolized modified lignin-based channeling sealing agent.
Preferably, the method comprises the steps of,
the pH value is adjusted to 7-11.
In the invention, whether the pH value needs to be regulated depends on the condition of the pH value in the channeling sealing system; if the pH value of the channeling sealing system is within the above range, the pH value may not be adjusted.
The pH regulator used for regulating the pH value can be acid and alkaline substances commonly used in the prior art for regulating the pH value; preferably, the pH regulator is at least one selected from dilute hydrochloric acid, dilute sulfuric acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate and ammonia water.
In the invention, the specific substances and the dosage of the added pH regulator are correspondingly selected and adjusted according to the acid and alkali conditions of the channeling sealing system, so that the pH value in the channeling sealing system can be within the limited pH value range.
Preferably, the content of the pH regulator is 0.1-1.5wt% based on 100% of the total weight of the raw materials; more preferably 0.5 to 1.2wt%.
The invention further aims to provide the application of the phenolized modified lignin-based channeling sealing agent in heavy oil exploitation.
Compared with the prior art, the invention has the following advantages:
the viscosity of the channeling sealing agent is 9.3-21.6 mPa.s at normal temperature (25 ℃), and the channeling sealing agent has good pumpability; the adhesive can be controllably formed into adhesive (1.5-120 h) within a wider temperature range (100-300 ℃), and the strength is between 0.071 and 0.086MPa; and the gel is not broken at the high temperature of 300 ℃ for 60 days, the dehydration rate is less than 4.9%, the plugging rate is higher than 99.06%, the steam channeling channel is effectively plugged for a long time, and the high-efficiency development of the heavy oil reservoir is realized.
The channeling sealing agent expands the temperature application range, has higher strength, and has the characteristics of large blocking strength, wide application range, high blocking efficiency and the like.
The channeling sealing agent adopts the modified phenolized lignin, can effectively reduce the dosage of lignin and a cross-linking agent in the existing system, reduces the production cost of the channeling sealing agent, meets the requirements of site construction on performance and economy, and has higher practicability.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw material sources are as follows:
the enzymatically hydrolyzed lignin was purchased from Shandong Longli Biotechnology Co., ltd, and the lignin content was 94.8wt%.
Alkali lignin was purchased from carbofuran technologies.
The amide thickener (AM/AMPS copolymer) was purchased from Shandong Bao Mohs Biochemical Co., ltd, and had an effective content of about 88% by weight and a weight average molecular weight of 1500 ten thousand. The amide thickener commonly used in the art is white particles in appearance, contains less than 12wt% of water and has an effective content of more than 88wt%.
The cross-linking agent is purchased from Shandong east chemical industry Co., ltd, and is DHY-20 type water-soluble phenolic resin cross-linking agent with the effective content of about 50wt%.
Phenol, resorcinol, potassium hydroxide, diethyl ether were purchased from carbofuran technologies.
Other raw materials in the channeling sealing agent are all conventional commercial products.
The testing method comprises the following steps:
initial viscosity measurement:
viscosity was measured using a Brookfield DV-III viscometer.
Intensity test:
the colloid strength is tested by adopting a breakthrough vacuum degree method, and the specific operation is as follows: the gel is put into a test bottle of a breaking vacuum degree experiment device, a 1mL pipette tip part is inserted into a position 1cm below the surface of the gel, a vacuum pump is started, a knob is slowly adjusted to increase the system vacuum degree, when air breaks through the gel, the maximum reading of the vacuum degree on a vacuum meter, namely the breaking vacuum degree of the gel, is repeatedly measured for 3 times, and the arithmetic average value is taken as the final strength value.
And (3) plugging rate test:
the simulated core (diameter of core is 25mm, length is 600 mm) is filled, and vacuuming and water saturation are carried out. Firstly, injecting water into the rock core at a certain flow rate, and measuring the permeability (k) before the rock core is plugged 0 ) The method comprises the steps of carrying out a first treatment on the surface of the Then under the condition of gas-liquid ratio of 1:1, the injection speed of 2mL/min is injected into the coreInjecting different channeling sealing agents at a certain ratio, heating a heating sleeve to 300 ℃ after stabilizing (gelling), and performing subsequent steam displacement; finally, the permeability (k') of the core after plugging is measured by water injection. The plugging rate is used as a parameter for representing the plugging effect of the channeling agent, and the calculation formula of the plugging rate is as followsWherein k is 0 To block the permeability before 2 The method comprises the steps of carrying out a first treatment on the surface of the k' is the permeability after plugging, μm 2 。
Dehydration rate test: after the reaction of the high-temperature stability test at 300 ℃, the volume of the free water outside the colloid in the reactor is measured, the dehydration rate is the ratio of the volume of the free water to the total volume of the gel forming liquid, and the volumes are all measured at room temperature.
Preparation example 1
Preparation of phenolized lignin FL-1
(1) 79.14g of water and 2.83g of a base catalyst KOH are added into a three-neck flask with a stirrer and a condenser at room temperature, and are uniformly stirred to prepare a KOH solution;
(2) Then heating the system to the set temperature of 85 ℃, sequentially adding 14.31g of enzymolysis lignin and 3.72g of phenol under stirring, continuously stirring, heating, refluxing, and reacting for 0.5h;
(3) After the reaction is finished, hydrochloric acid is added to adjust the pH value to 3.0, so that a product is separated out, and the product phenolized lignin FL-1 is obtained through centrifugal separation, diethyl ether 3 times of washing and vacuum drying.
Preparation example 2
Preparation of phenolized lignin FL-2
(1) 82.52g of water and 2.36g of alkali catalyst NaOH are added into a three-neck flask with a stirrer and a condenser at room temperature, and stirred uniformly to prepare NaOH solution;
(2) Then the system is heated to the set temperature of 70 ℃, 11.89g of enzymolysis lignin and 3.23g of resorcinol are added in sequence under stirring, stirring is continued, heating and reflux are carried out, and the reaction is carried out for 1.5h;
(3) After the reaction is finished, hydrochloric acid is added to adjust the pH value to 2.5, so that a product is separated out, and the product phenolized lignin FL-2 is obtained through centrifugal separation, diethyl ether 3 times of washing and vacuum drying.
Preparation example 3
Preparation of phenolized lignin FL-3
(1) 81.14g of water and 2.83g of alkali catalyst NaOH are added into a three-neck flask with a stirrer and a condenser at room temperature, and stirred uniformly to prepare NaOH solution;
(2) Then heating the system to 75 ℃, sequentially adding 12.31g of alkali lignin and 3.72g of resorcinol under stirring, continuously stirring, heating, refluxing, and reacting for 1.5h;
(3) After the reaction is finished, hydrochloric acid is added to adjust the pH value to 3.0, so that a product is separated out, and the product phenolized lignin FL-3 is obtained through centrifugal separation, diethyl ether 3 times of washing and vacuum drying.
Example 1
0.08g of amide thickener (AM/AMPS copolymer) is dissolved in 80g of formulated water with the mineralization degree of 8000mg/L, and stirred at the rotating speed of 500r/min until the mixture is uniformly dissolved; then adding 2.8g of phenolized lignin FL-2, 0.035g of titanium sulfate, 0.023g of thiourea and 1.8g of phenolic resin, adding sodium hydroxide to adjust the pH to 10, adding formulated water with the mineralization degree of 8000mg/L to quantitatively reach 100g, and stirring uniformly to obtain the high-temperature channeling sealing agent. The initial viscosity of the high-temperature channeling sealing agent is 16.5 mPa.s at 25 ℃; the strength reaches 0.086MPa after gel forming under the condition of 125 ℃; and the gel is not broken in the temperature of 300 ℃ for 60 days, and the dehydration rate is 2.3 percent; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 99.32%.
Example 2
0.05g of amide thickener (AM/AMPS copolymer) is dissolved in 80g of preparation water with the mineralization degree of 23000mg/L, and stirred at the rotating speed of 500r/min until the mixture is uniformly dissolved; then adding 2g of phenolized lignin FL-2, 0.02g of titanium chloride, 0.01g of thiourea and 0.8g of phenolic resin, adding sodium hydroxide to adjust the pH to 10.5, adding prepared water with the mineralization degree of 23000mg/L to quantitatively reach 100g, and uniformly stirring to obtain the high-temperature channeling sealing agent. The initial viscosity of the high-temperature channeling sealing agent is 11.2 mPa.s at 25 ℃; the strength reaches 0.073MPa after the gel is formed at 180 ℃; and the gel is not broken in the temperature of 300 ℃ for 60 days, and the dehydration rate is 4.8%; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 99.03%.
Example 3
0.07g of amide thickener (AM/AMPS copolymer) is dissolved in 80g of preparation water with the mineralization degree of 12000mg/L, and stirred at the rotating speed of 500r/min until the mixture is uniformly dissolved; then adding 2.6g of phenolized lignin FL-1, 0.032g of manganese chloride, 0.026g of thiourea and 1.7g of phenolic resin, adding sodium hydroxide to adjust the pH value to 9, adding the prepared water with the mineralization degree of 12000mg/L to quantitatively reach 100g, and uniformly stirring to obtain the high-temperature channeling sealing agent. The initial viscosity of the high-temperature channeling sealing agent is 15.2 mPa.s at 25 ℃; the strength reaches 0.083MPa after gel forming at 100 ℃; and the gel is not broken in the temperature of 300 ℃ for 60 days, and the dehydration rate is 3.1 percent; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 99.24%.
Example 4
0.1g of amide thickener (AM/AMPS copolymer) is dissolved in 80g of preparation water with the mineralization degree of 25000mg/L, and stirred at the rotating speed of 500r/min until the mixture is uniformly dissolved; then adding 3g of phenolized lignin FL-1, 0.04g of manganese sulfate, 0.03g of thiourea and 2g of phenolic resin, adding sodium hydroxide to adjust the pH value to 9, adding the prepared water with the mineralization degree of 25000mg/L to quantitatively reach 100g, and uniformly stirring to obtain the high-temperature channeling sealing agent. The initial viscosity of the high-temperature channeling sealing agent is 21.6 mPa.s at 25 ℃; the strength reaches 0.085MPa after the gel is formed at 150 ℃; and the gel is not broken in the temperature of 300 ℃ for 60 days, and the dehydration rate is 2.8%; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 99.41%.
Example 5
The preparation method of example 5 was the same as that of example 1, except that phenolated lignin FL-3 prepared in preparation example 3 was used. The initial viscosity of the high-temperature channeling sealing agent is 17.4 mPa.s at 25 ℃; the strength reaches 0.079MPa after the gel is formed at 125 ℃; and the gel is not broken in the temperature of 300 ℃ for 60 days, and the dehydration rate is 4.6 percent; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 99.18%.
Comparative example 1
Experiments were conducted according to the method of example 1, except that phenolated lignin FL-2 was replaced with non-phenolated modified enzymatic lignin, the initial viscosity of the obtained channeling sealing agent was 14.8 mPa.s at 25 ℃, the strength after gelling at 125 ℃ was 0.026MPa, the gel had been broken for 60 days, and the dehydration rate was 34.3%; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 80.44%.
Comparative example 2
Experiments were conducted according to the method of example 2, except that phenolated lignin FL-2 was replaced with non-phenolated modified enzymatic lignin, the initial viscosity of the obtained channeling sealing agent was 10.1 mPa.s at 25℃and the strength after gelling at 180℃was 0.016MPa, and the gel breaking and dehydration rates were 47.3% after 60 days; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 73.73%.
Comparative example 3
Experiments were conducted according to the method of example 3, except that phenolated lignin FL-1 was replaced with non-phenolated modified enzymatic lignin, the initial viscosity of the obtained channeling sealing agent was 13.4 mPa.s at 25 ℃, the strength after gelling at 100 ℃ was 0.025MPa, and the gel breaking and dehydration rate was 32.1% after 60 days; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 83.64%.
Comparative example 4
Experiments were conducted according to the method of example 4, except that phenolated lignin FL-1 was replaced with non-phenolated modified enzymatic lignin, the initial viscosity of the obtained channeling sealing agent was 19.9 mPa.s at 25 ℃, the strength after gelling at 150 ℃ was 0.034MPa, and the gel breaking and dehydration rate was 30.4% after 60 days; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 84.87%.
Comparative example 5
Experiments were conducted according to the method of example 5, except that phenolated lignin FL-3 was replaced with alkali lignin which was not phenolated and modified, the initial viscosity of the obtained channeling blocking agent was 16.1 mPa.s at 25 ℃, the strength after gelling at 125 ℃ was 0.028MPa, and the gel breaking and dehydration rate was 35.2% after 60 days; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 81.02%.
Comparative example 6
The difference compared to example 1 is that the phenolized lignin FL-2 is replaced by FL-4. The FL-4 and FL-2 preparation processes are basically the same, the difference is that the concentration of enzymolysis lignin is 30wt%, the initial viscosity of the obtained channeling sealing agent is 15.2 mPa.s at 25 ℃, the strength after gel formation is 0.062MPa at 125 ℃, gel breaking is carried out in 60 days, and the dehydration rate is 15.1%; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 84.33%.
Comparative example 7
The difference compared to example 1 is that the phenolized lignin FL-2 is replaced by FL-5. The FL-5 and FL-2 preparation processes are basically the same, the difference is that the addition amount of the enzymolysis lignin is kept unchanged, the addition amount of resorcinol is reduced, the mass ratio of resorcinol to the enzymolysis lignin is 0.1:1, the initial viscosity of the obtained channeling sealing agent is 15.1 mPa.s at 25 ℃, the strength after gelling at 125 ℃ is 0.065MPa, the gelling has been carried out for 60 days, and the dehydration rate is 11.9%; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 85.65%.
Comparative example 8
The difference compared to example 1 is that the phenolized lignin FL-2 is replaced by FL-6. The FL-6 and FL-2 preparation processes are basically the same, the difference is that the addition amount of enzymolysis lignin is kept unchanged, the addition amount of alkali catalyst is reduced, the mass ratio of alkali catalyst NaOH to enzymolysis lignin is 0.1:1, the initial viscosity of the obtained channeling sealing agent is 14.3 mPa.s at 25 ℃, the strength after gel formation is 0.059MPa at 125 ℃, gel breaking is carried out in 60 days, and the dehydration rate is 17.2%; and (5) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 78.56%.
Comparative example 9
The difference compared to example 1 is that the phenolized lignin FL-2 is replaced by FL-7. The FL-7 and FL-2 preparation processes are basically the same, the difference is that the heating temperature of the reaction system is 40 ℃, the initial viscosity of the obtained channeling sealing agent is 14.7 mPa.s at 25 ℃, the strength after gel forming is 0.042MPa at 125 ℃, gel breaking is carried out in 60 days, and the dehydration rate is 26.1%; and (3) performing plugging test on the obtained channeling sealing agent, wherein the plugging rate is 83.14%.
As can be seen from the comparison examples and the comparison examples, the viscosity of the high-temperature channeling sealing system is 9.3-21.6 mPa.s at normal temperature (25 ℃), and the high-temperature channeling sealing system has good pumpability; the adhesive can be controllably formed into adhesive (1.5-120 h) within a wider temperature range (100-300 ℃), and the strength is between 0.071 and 0.086MPa; and the gel is not broken at the high temperature of 300 ℃ for 60 days, the dehydration rate is less than 4.9%, the plugging rate is higher than 99.06%, the steam channeling channel is effectively plugged for a long time, and the high-efficiency development of the heavy oil reservoir is realized. The system expands the temperature application range, has higher strength, has the characteristics of large blocking strength, wide application range, high blocking efficiency and the like, effectively reduces the concentration of the main agent and the cross-linking agent, reduces the production cost of the channeling sealing agent, meets the requirements of site construction performance and economy, and has higher practicability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. The phenolic modified lignin-based channeling sealing agent is characterized by being prepared from the following raw materials in parts by weight:
phenolated lignin, thickener, cross-linker, modifier, stabilizer and formulation water;
based on the total weight of the raw materials as 100 percent,
the content of phenolized lignin is 1.5-3.5wt%;
the content of the thickener is 0.001-0.15wt%;
the content of the cross-linking agent is 0.02-2.5wt%;
the content of the modifier is 0.01-0.05wt%;
the content of the stabilizer is 0.001-0.05wt%;
the cross-linking agent is at least one of water-soluble phenolic resin prepared by taking phenol, homologs thereof and aldehydes as raw materials; the modifier is selected from Mn 2+ 、Ti 4+ At least one of the soluble salts of (a).
2. The phenolized modified lignin-based channeling sealing agent of claim 1, wherein:
based on the total weight of the raw materials as 100 percent,
the phenolated lignin content is 2-3wt%;
the content of the thickener is 0.05-0.1wt%;
the content of the cross-linking agent is 0.8-2wt%;
the content of the modifier is 0.02-0.04wt%;
the content of the stabilizer is 0.01-0.03wt%.
3. The phenolized modified lignin-based channeling sealing agent of claim 1, wherein:
the preparation method of the phenolized lignin comprises the following steps:
adding lignin and phenol into a base catalyst solution, carrying out contact reaction under heating and reflux conditions to obtain a solution containing phenolated lignin, cooling to room temperature, adjusting the pH value to be acidic, and purifying to obtain the phenolated lignin.
4. The phenolized modified lignin-based channeling blocking agent of claim 3, wherein:
the lignin is at least one selected from alkali lignin, enzymolysis lignin, chlorination lignin, steam explosion lignin and sulfur lignin; and/or the number of the groups of groups,
the phenol is selected from at least one of phenol, hydroquinone, resorcinol and catechol; and/or the number of the groups of groups,
the alkali catalyst is at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
5. The phenolized modified lignin-based channeling blocking agent of claim 3, wherein:
in the reaction system of the contact reaction,
the concentration of the lignin is 10-15wt%;
the mass ratio of the phenol to the lignin is 0.2-0.4:1;
the mass ratio of the alkali catalyst to the lignin is 0.12-0.3:1;
heating at 70-85deg.C for 0.5-2 hr;
and regulating the pH value to 2-3.
6. The phenolized modified lignin-based channeling sealing agent of claim 1, wherein:
the thickener is an amide thickener; the weight average molecular weight of the thickener is 500-3000 ten thousand; and/or the number of the groups of groups,
the cross-linking agent is at least one of water-soluble phenolic resin prepared from phenol, homologs thereof and aldehydes serving as raw materials, and the effective content is more than 38wt%.
7. The phenolized modified lignin-based channeling sealing agent of claim 6, wherein:
the thickening agent is at least one of acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer; the weight average molecular weight of the thickener is 1000-2000 ten thousand.
8. The phenolized modified lignin-based channeling sealing agent of claim 1, wherein:
the modifier is at least one of titanium sulfate, titanium chloride, manganese sulfate or manganese chloride; and/or the number of the groups of groups,
the stabilizer is at least one selected from sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, isoascorbic acid or thiourea; and/or the number of the groups of groups,
the mineralization degree of the prepared water is lower than 100000mg/L.
9. The method for preparing a phenolized modified lignin-based channeling blocking agent according to any one of claims 1 to 8, comprising the steps of:
adding a thickening agent into the prepared water for full dissolution, adding the phenolized lignin, a cross-linking agent, an improver and a stabilizer, adjusting the pH value, and uniformly stirring to obtain the phenolized modified lignin-based channeling sealing agent.
10. The method for preparing the phenolized modified lignin-based channeling sealing agent according to claim 9, wherein the method comprises the steps of,
the pH value is adjusted to 7-11.
11. Use of the phenolized modified lignin-based channeling sealing agent according to any of claims 1-8 in heavy oil recovery.
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| CN1204677A (en) * | 1998-06-05 | 1999-01-13 | 中国科学院广州化学研究所 | Manufacturing method for oil deposit water-stop gelatinizing liquid |
| CN102659992A (en) * | 2012-05-11 | 2012-09-12 | 黄山学院 | Phenolic lignin-based modified foaming phenolic resin, foamed plastic and preparation method of phenolic lignin-based modified foaming phenolic resin |
| CN104474966A (en) * | 2014-12-30 | 2015-04-01 | 福建清源科技有限公司 | Modified lignin-based dispersing agent and preparation method thereof |
| CN112521624A (en) * | 2019-12-31 | 2021-03-19 | 济南圣泉集团股份有限公司 | Phenolated lignin, amphoteric lignin emulsifier, emulsified asphalt and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1204677A (en) * | 1998-06-05 | 1999-01-13 | 中国科学院广州化学研究所 | Manufacturing method for oil deposit water-stop gelatinizing liquid |
| CN102659992A (en) * | 2012-05-11 | 2012-09-12 | 黄山学院 | Phenolic lignin-based modified foaming phenolic resin, foamed plastic and preparation method of phenolic lignin-based modified foaming phenolic resin |
| CN104474966A (en) * | 2014-12-30 | 2015-04-01 | 福建清源科技有限公司 | Modified lignin-based dispersing agent and preparation method thereof |
| CN112521624A (en) * | 2019-12-31 | 2021-03-19 | 济南圣泉集团股份有限公司 | Phenolated lignin, amphoteric lignin emulsifier, emulsified asphalt and preparation method |
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