CN112159651A - Multifunctional thickening agent and preparation method thereof - Google Patents
Multifunctional thickening agent and preparation method thereof Download PDFInfo
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- CN112159651A CN112159651A CN202011190119.1A CN202011190119A CN112159651A CN 112159651 A CN112159651 A CN 112159651A CN 202011190119 A CN202011190119 A CN 202011190119A CN 112159651 A CN112159651 A CN 112159651A
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/665—Compositions based on water or polar solvents containing inorganic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/28—Friction or drag reducing additives
Abstract
The invention discloses a multifunctional thickening agent and a preparation method thereof, wherein the raw materials comprise the following components in parts by weight: 30-50 parts of water-soluble thickening agent, 45-55 parts of acetone glycerol, 3-5 parts of D-limonene and 1-2 parts of suspending agent. The multifunctional thickening agent has excellent resistance reducing, salt resisting, sand carrying and viscosity changing capabilities, can realize on-line viscosity changing operation, has the advantages of powder thickening agent and emulsion thickening agent, and is convenient to use; the stability of the obtained ultra-dispersed system is greatly improved by adopting a water-soluble dispersant to match with D-limonene and matching with the specially-made modified bentonite.
Description
Technical Field
The invention relates to the field of thickening agents, in particular to a multifunctional thickening agent and a preparation method thereof.
Background
Shale Gas (Shale Gas) refers to unconventional natural Gas existing in an adsorbed or free state in organic matter-rich Shale and an interlayer thereof, and is mainly composed of methane, so that the Shale Gas is a clean and efficient energy resource and chemical raw material.
The shale reservoir matrix permeability is extremely low, natural productivity does not exist under most conditions, and the reservoir must be subjected to large-scale fracturing modification to improve the formation permeability by a manual method. The shale reservoir has the characteristics of high brittleness index and natural microcrack development, the transformation adopts a volume fracturing idea of large discharge capacity, large liquid amount and low sand concentration, and the slickwater fracturing liquid with low viscosity is used for communicating natural fractures to form a complex fracture network, so that the effective transformation volume is increased. The thickening agent is the most main additive in the slickwater fracturing fluid, and the friction resistance of the fracturing fluid is reduced by means of the high-molecular turbulence drag reduction effect, so that the construction discharge capacity is improved, and the pump pressure is reduced.
Current operating environments and technologies have the following requirements for thickener performance:
1) shale gas volume fracturing creates a complex fracture network through large displacement, and has high requirement on drag reduction rate. Particularly for deep shale gas, the pressure window is narrow, and products with higher drag reduction rate are needed;
2) the thickening agent has high dissolution speed in water, takes effect immediately, avoids delay of drag reduction effect caused by overlong dissolution time, brings higher construction friction resistance, and increases the load of equipment;
3) the multilevel alternate injection of the variable-viscosity fracturing fluid is very effective for improving the complexity of cracks, and the thickening agent is required to meet the requirement that the real-time switching of different viscosity fluids can be realized by adjusting the addition amount so as to realize the online variable-viscosity operation;
4) the shale reservoir matrix has extremely low permeability, and requires a thickening agent to have small influence on the seepage capability of the reservoir and low damage rate;
5) the thickening agent has good stability, can be measured on line and is convenient to use.
The thickeners commonly used at present are of the powder type and of the oil-based emulsion type. The powder type thickening agent has high drag reduction rate, strong tackifying capability and good sand carrying property, but because the dissolution speed is low and the on-line metering is difficult, the liquid needs to be prepared in advance, and the lower efficiency is difficult to meet the requirement of continuous operation. And once the liquid preparation is finished, the viscosity can not be adjusted, and the process requirement of multistage alternate injection of the variable-viscosity fracturing liquid can not be met. The oil-based emulsion type thickening agent has the advantages of high dissolution speed, convenient use and accurate metering, and can meet the large-scale continuous online 'viscosity-changing' operation of 'mixing and injecting' immediately. However, the emulsion polymerization process has high difficulty, low effective content and low molecular weight, has far lower resistance, salt resistance, sand carrying capacity and viscosity changing capacity than that of a powder thickener, has poor emulsion stability, and is easy to break emulsion after being placed for a long time, so that the product is deteriorated and the use is influenced.
Furthermore, there are studies showing that: the slippery water prepared from the powder type thickening agent often contains a large amount of incompletely dissolved swelling polymer colloidal particles, and the colloidal particles can block pores and microcracks of a reservoir, so that the permeability of the reservoir is reduced, and the productivity is influenced. The oil-based emulsion drag reducer contains a large amount of mineral oil, the oil phase is adsorbed in the stratum to easily cause wettability reversal, the capillary resistance during flowback is increased, microemulsion is possibly generated under high-speed shearing to cause a 'Jamin effect', and the final flowback rate and the capacity are influenced.
In order to better meet the requirements of practical application, the advantages of two products, namely a powder thickening agent and an emulsion thickening agent, are combined, and patent CN110317600A and the like proposes a scheme of dispersing the powder thickening agent, such as polyacrylamide polymers and the like, in mineral oil such as white oil and preparing the powder thickening agent into a uniform slurry-like thickening agent by matching with a dispersing agent and a suspending agent. The thickening agent has high dissolving speed, and has better performances of viscosity change, resistance reduction, sand carrying and the like; the liquid has good fluidity, can be directly pumped by a pump, and realizes online metering operation. However, the products contain a large amount of mineral oil, and the problem of damage to the stratum is serious and can not be ignored, and further improvement is still needed.
Disclosure of Invention
The invention mainly solves the technical problem of providing the multifunctional thickening agent for the shale gas exploitation hydraulic fracturing, and the thickening agent has excellent properties of viscosity change, drag reduction, sand carrying and the like, has little damage to stratum, can be used for on-line metering operation, and has excellent stability.
In order to solve the problem of damage of mineral oil to the formation, the inventors tried to use a water-soluble dispersion medium, resulting in a problem that dispersibility and stability of the product are deteriorated. For example, in patent CN11592869A, a water-soluble solvent of polyol ether or polyol ester is used as a dispersion medium, but the stability of the obtained product is poor, and the liquid-out rate of the stability test of most examples is above 10% and 15%. One result caused by poor product stability is that the powder thickening agent is in a coarse dispersion state in a dispersion medium, the hydration capability of the powder thickening agent is poor due to a larger dispersion scale, the dissolution speed is slow, fish eyes or swelling polymer colloidal particles which are not completely dissolved are easily generated, and the powder thickening agent is greatly damaged to a reservoir stratum after being injected into a stratum; another result is that the powder thickener in the product is prone to agglomeration and sedimentation, resulting in non-uniformity of the product, and the bulk viscosity increases dramatically, which makes pumping difficult in field use.
It is seen that in order to solve the problem of damage to the formation caused by mineral oil, it is not feasible to simply replace the oily dispersant with the aqueous dispersant, and the dispersion and stability of the system must be considered simultaneously when an aqueous dispersion medium is used.
After long-term research and continuous experiments, the inventor of the present invention finds that, after the acetone glycidol which is a water-soluble dispersion medium is used and D-limonene is added as a dispersing agent and is combined with a special SDS modified bentonite suspending agent, a super-dispersion system can be formed together with a powder thickening agent, so that the product stability is greatly improved. The problem of damage of mineral oil to the stratum is solved, the problem of product stability is solved, and the method has great field application value.
In order to solve the technical problems, the invention adopts a technical scheme that:
the multifunctional thickening agent is provided, and the raw materials comprise the following components in parts by weight: 30-50 parts of water-soluble thickening agent, 45-55 parts of acetone glycerol, 3-5 parts of D-limonene and 1-2 parts of suspending agent.
The multifunctional thickening agent is added with D-limonene, so that the dispersion stability of the thickening agent can be improved, the dissolving speed of a product can be increased, and the online 'sticky' operation can be realized.
Further, the raw materials comprise the following components in parts by weight: 30-43 parts of water-soluble thickening agent, 50-55 parts of acetone condensed glycerol, 4-5 parts of D-limonene and 1.5-2 parts of suspending agent.
Further, the raw materials comprise the following components in parts by weight: 43 parts of water-soluble thickening agent, 50 parts of acetone condensed glycerol, 5 parts of D-limonene and 2 parts of suspending agent.
Further, the suspending agent is SDS modified bentonite, and the raw materials of the SDS modified bentonite comprise the following components in parts by weight: 0.5-1.5 parts of sodium carbonate, 95-105 parts of water, 1-3 parts of sodium dodecyl sulfate and 9-11 parts of bentonite.
Further, the SDS modified bentonite comprises the following raw materials in parts by weight: 1.0-1.5 parts of sodium carbonate, 95-99 parts of water, 2-3 parts of sodium dodecyl sulfate and 9-11 parts of bentonite.
Further, the SDS modified bentonite comprises the following raw materials in parts by weight: 1.5 parts of sodium carbonate, 95 parts of water, 3 parts of sodium dodecyl sulfate and 11 parts of bentonite.
Further, the particle size of the suspending agent is not less than 150 meshes, preferably not less than 180 meshes, and more preferably not less than 200 meshes.
Further, the water-soluble thickening agent is selected from acrylamide homopolymer and/or acrylamide copolymer, and has a molecular weight of 800-2500 ten thousand, preferably 1000-2000 ten thousand, and more preferably 1200-1800 ten thousand.
The invention also provides a preparation method of the multifunctional thickening agent, which comprises the following steps:
(1) mixing and emulsifying part of the acetone glycerin in the formula amount with a suspending agent to obtain a suspension;
(2) mixing the rest acetone condensed glycerol with a water-soluble thickening agent, and mixing with D-limonene to obtain a polymer dispersion liquid;
(3) mixing the suspension prepared in the step (1) with the polymer dispersion liquid obtained in the step (2).
Further, in the step (1), the part of the acetone glycidol accounts for 5-20%, preferably 8-12%, preferably 8-10%, and more preferably 8% of the total usage amount of the formula.
Further, in the step (1), the emulsifying condition is emulsifying at 50-70 ℃ for 20-60 min, preferably emulsifying at 55-65 ℃ for 25-35 min, preferably emulsifying at 55-60 ℃ for 30-35 min, and more preferably emulsifying at 55 ℃ for 35 min.
Further, the mixing manner with the D-limonene is that the D-limonene is added into the mixture of the acetone condensed glycerol and the water-soluble thickening agent in batches; further, the D-limonene is added in batches within 20-50 min, preferably within 30-40 min, preferably within 30-35 min, and more preferably within 30 min.
The batch addition refers to non-one-time addition, and can be realized by adding the raw materials at a certain or different feeding speed within a period of time, or by dividing the raw materials to be added into a plurality of parts and adding the parts for a plurality of times within a certain period of time.
In an embodiment of the invention, the D-limonene is added in a dropwise manner.
Further, the preparation method also comprises the following steps of:
a. mixing water and sodium carbonate, then mixing with sodium dodecyl sulfate and bentonite, and carrying out ultrasonic treatment for 2-5 h at 50-70 ℃ under the condition of 30-50 KHz to obtain a modified bentonite semi-finished product I; preferably, ultrasonic treatment is carried out for 2.5-3.5 h under the conditions of 55-65 ℃ and 35-45 KHz; preferably, the ultrasonic treatment is carried out for 3.0-3.5 h under the conditions of 55-60 ℃ and 35-40 KHz; more preferably, ultrasonic treatment is carried out for 3.5h under the conditions of 55 ℃ and 35 KHz;
b. filtering and drying the modified bentonite semi-finished product I to obtain a modified bentonite semi-finished product II;
c. and grinding the modified bentonite semi-finished product II and sieving the ground product II with a 150-200-mesh sieve, preferably sieving the ground product II with a 180-200-mesh sieve, and more preferably sieving the ground product II with a 200-mesh sieve.
The invention has the beneficial effects that:
(1) the multifunctional thickening agent disclosed by the invention forms a super-dispersion system through the synergistic cooperation of the acetone glycerol, the D-limonene and the SDS modified bentonite, the dissolving speed is high, and the stability of the thickening agent is obviously improved.
(2) The multifunctional thickening agent combines the advantages of the powder thickening agent and the emulsion thickening agent, can realize quick dissolution and on-line viscosity-changing operation, and has better performances of thickening, resistance reduction, sand carrying and the like. Meanwhile, the problem that mineral oil damages the stratum and the problem that a dispersion system is unstable due to the adoption of a water-soluble dispersion medium are solved.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polyacrylamide products used in this example were: anionic polyacrylamide (Hebei Tianshi chemical Co., Ltd.), with a molecular weight of 1200-1800 ten thousand.
Example 1
1.1 raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1 part; water: 99 parts of a mixture; sodium dodecyl sulfate: 2 parts of (1); bentonite: 10 parts of (A);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 30 parts of (1); 55 parts of acetone condensed glycerol; d-limonene: 4 parts of a mixture; suspending agent: 1.5 parts; the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
1.2 the preparation method comprises the following steps:
the method comprises the following steps:
s1: preparing SDS modified bentonite;
(1) adding water and sodium carbonate into a reaction vessel, adding sodium dodecyl sulfate and bentonite into the reaction vessel after the sodium carbonate is dissolved, starting stirring, heating to 60 ℃, and maintaining the temperature at 60 ℃ and the frequency at 40KHZ for ultrasonic oscillation dispersion for 3 hours; obtaining a modified bentonite semi-finished product I;
(2) filtering the modified bentonite semi-finished product I obtained in the step (1), and drying at the temperature of 120 ℃ until the water content is less than 5%, so as to obtain a modified bentonite semi-finished product II;
(3) grinding the semi-finished product II of the modified bentonite obtained in the step (2), and then screening the ground semi-finished product II through a 200-mesh vibrating screen to obtain a filtrate, namely a finished product of the SDS modified bentonite;
s2: adding acetone glycerin into the reaction kettle, wherein the addition amount of the acetone glycerin is 10 percent of the total weight of the acetone glycerin; starting a stirring and emulsifying pump (the stirring rotating speed is 150r/min, the emulsifying and shearing rotating speed is 2500r/min), adding a suspending agent into the reaction kettle according to the proportion, heating to 60 ℃, keeping the temperature at 60 ℃, shearing and emulsifying for 30 minutes (the emulsifying and shearing rotating speed is 2500r/min), stopping heating, cooling to 25 ℃ to obtain a suspension, and transferring the suspension into a high-level tank;
s3: adding the rest acetone glycidol into a reaction kettle, adding a water-soluble thickening agent into the reaction kettle, performing material circulating shearing for 30min (the rotating speed of emulsifying shearing is 2500r/min) through an emulsifying pump, uniformly dropwise adding D-limonene into the reaction kettle for 35min under the conditions of keeping stirring and circulating shearing (the rotating speed of stirring is 150r/min, and the rotating speed of emulsifying shearing is 2500r/min), and obtaining a polymer dispersion liquid;
s4: adding the suspension prepared in the step S2 into the polymer dispersion prepared in the step S3, and performing material circulating shearing through an emulsification pump for 60min (the rotation speed of emulsification shearing is 2500 r/min).
Example 2
2.1, raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1 part; water: 99 parts of a mixture; sodium dodecyl sulfate: 2 parts of (1); bentonite: 10 parts of (A);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 50 parts of a mixture; acetone glycerol condensation: 45 parts of (1); d-limonene: 3 parts of a mixture; suspending agent: 1 part, the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
2.2 the preparation method comprises the following steps:
the method comprises the following steps:
s1: preparing SDS modified bentonite;
(1) adding water and sodium carbonate into a reaction vessel, adding sodium dodecyl sulfate and bentonite into the reaction vessel after the sodium carbonate is dissolved, starting stirring, heating to 65 ℃, keeping the temperature at 65 ℃ and carrying out ultrasonic oscillation dispersion at the frequency of 45KHZ for 2.5 hours; obtaining a modified bentonite semi-finished product I;
(2) filtering the modified bentonite semi-finished product I obtained in the step (1), and drying at the temperature of 120 ℃ until the water content is less than 5%, so as to obtain a modified bentonite semi-finished product II;
(3) grinding the semi-finished product II of the modified bentonite obtained in the step (2), and then screening the ground semi-finished product II through a 200-mesh vibrating screen to obtain a filtrate, namely a finished product of the SDS modified bentonite;
s2: adding acetone glycerin into the reaction kettle, wherein the addition amount of the acetone glycerin is 12% of the total weight of the acetone glycerin; starting a stirring and emulsifying pump (the stirring rotating speed is 130r/min, the emulsifying and shearing rotating speed is 3000r/min), adding the suspending agent into the reaction kettle according to the proportion, heating to 65 ℃, keeping the temperature at 65 ℃, shearing and emulsifying for 25 minutes (the emulsifying and shearing rotating speed is 3000r/min), stopping heating, cooling to 30 ℃ to obtain a suspension, and transferring the suspension into a high-level tank;
s3: adding the rest acetone glycidol into a reaction kettle, adding a water-soluble thickening agent into the reaction kettle, performing material circulating shearing for 35min (the rotating speed of emulsifying shearing is 3000r/min) through an emulsifying pump, uniformly dropwise adding D-limonene into the reaction kettle for 40min under the conditions of keeping stirring and circulating shearing (the rotating speed of stirring is 130r/min, and the rotating speed of emulsifying shearing is 3000r/min), and obtaining a polymer dispersion liquid;
s4: and (4) adding the suspension prepared in the step S2 into the polymer dispersion prepared in the step S3, and performing material circulating shearing for 65min through an emulsification pump (the rotating speed of emulsification shearing is 3000r/min), so as to obtain the multifunctional thickening agent.
Example 3
3.1 raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1 part; water: 99 parts of a mixture; sodium dodecyl sulfate: 2 parts of (1); bentonite: 10 parts of (A);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
3.2 the preparation method comprises the following steps:
the method comprises the following steps:
s1: preparing SDS modified bentonite;
(1) adding water and sodium carbonate into a reaction vessel, adding sodium dodecyl sulfate and bentonite into the reaction vessel after the sodium carbonate is dissolved, starting stirring, heating to 55 ℃, and maintaining the temperature at 55 ℃ and the frequency at 35KHZ for ultrasonic oscillation dispersion for 3.5 hours; obtaining a modified bentonite semi-finished product I;
(2) filtering the modified bentonite semi-finished product I obtained in the step (1), and drying at the temperature of 120 ℃ until the water content is less than 5%, so as to obtain a modified bentonite semi-finished product II;
(3) grinding the semi-finished product II of the modified bentonite obtained in the step (2), and then screening the ground semi-finished product II through a 200-mesh vibrating screen to obtain a filtrate, namely a finished product of the SDS modified bentonite;
s2: adding acetone glycerin into the reaction kettle, wherein the addition amount of the acetone glycerin is 8 percent of the total weight of the acetone glycerin; starting a stirring and emulsifying pump (the stirring rotating speed is 170r/min, the emulsifying and shearing rotating speed is 2300r/min), adding the suspending agent into the reaction kettle according to the proportion, heating to 55 ℃, keeping the temperature at 55 ℃, shearing and emulsifying for 35 minutes (the emulsifying and shearing rotating speed is 2300r/min), stopping heating, cooling to 20 ℃, obtaining a suspension, and transferring the suspension into a high-level tank;
s3: adding the rest acetone glycidol into a reaction kettle, simultaneously adding a water-soluble thickening agent into the reaction kettle, carrying out material circulating shearing for 25min (the rotating speed of emulsifying shearing is 2300r/min) through an emulsifying pump, uniformly dropwise adding D-limonene into the reaction kettle for 30min under the conditions of keeping stirring and circulating shearing (the rotating speed of stirring is 170r/min, and the rotating speed of emulsifying shearing is 2300r/min), and obtaining a polymer dispersion liquid;
s4: and (4) adding the suspension prepared in the step S2 into the polymer dispersion prepared in the step S3, and performing material circulating shearing through an emulsification pump for 55min (the rotation speed of emulsification shearing is 2300r/min) to obtain the multifunctional thickening agent.
Example 4
4.1 raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1.5 parts; water: 95 parts of (C); sodium dodecyl sulfate: 3 parts of a mixture; bentonite: 11 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
4.2 the preparation method comprises the following steps: the same as in example 3.
Example 5
5.1, raw materials:
preparing an SDS modified bentonite raw material:
0.5 part by weight; water: 105 parts of (A); sodium dodecyl sulfate: 1 part; bentonite: 9 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
5.2 the preparation method comprises the following steps: the same as in example 3.
Comparative example 1 solvent replacement
Raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1.5 parts; water: 95 parts of (C); sodium dodecyl sulfate: 3 parts of a mixture; bentonite: 11 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of ethylene glycol monomethyl ether; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
The preparation method comprises the following steps: the same as in example 3.
Comparative example 2 solvent replacement
Raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1.5 parts; water: 95 parts of (C); sodium dodecyl sulfate: 3 parts of a mixture; bentonite: 11 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of polyethylene glycol; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide (with the molecular weight of 2500 ten thousand), and the suspending agent adopts SDS modified bentonite.
The preparation method comprises the following steps: the same as in example 3.
Comparative example 3 solvent replacement
Raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1.5 parts; water: 95 parts of (C); sodium dodecyl sulfate: 3 parts of a mixture; bentonite: 11 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 23.5 parts of ethylene glycol monomethyl ether; and (3) pentanediol: 26.5 parts; d-limonene: 5 parts of a mixture; suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide (with the molecular weight of 2500 ten thousand), and the suspending agent adopts SDS modified bentonite.
The preparation method comprises the following steps: the same as in example 3.
Comparative example 4D replacement of limonene with carboxymethyl cellulose
Raw materials:
preparing an SDS modified bentonite raw material:
according to parts by weight, sodium carbonate: 1.5 parts; water: 95 parts of (C); sodium dodecyl sulfate: 3 parts of a mixture; bentonite: 11 parts of (1);
the preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; carboxymethyl cellulose: 2 parts of (1); suspending agent: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide, and the suspending agent adopts SDS modified bentonite.
The preparation method comprises the following steps: the same as in example 3.
Comparative example 5 use of ordinary Bentonite
The preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; d-limonene: 5 parts of a mixture; sodium bentonite: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide.
The preparation method comprises the following steps: the same as in example 3.
Comparative example 6 use of organobentonite
The preparation method of the multifunctional thickening agent comprises the following steps:
according to parts by weight, water-soluble thickening agent: 43 parts of a mixture; 50 parts of acetone condensed glycerol; d-limonene: 5 parts of a mixture; organic bentonite: 2 parts of (1); the water-soluble thickening agent adopts polyacrylamide.
The preparation method comprises the following steps: the same as in example 3.
The beneficial effects of the multifunctional thickener of the invention are verified by the following test examples:
the multifunctional thickeners prepared in examples 1 to 5 are sequentially noted as: sample 1, sample 2, sample 3, sample 4, sample 5; FR-WH is a Solvay FR-WH product, EM533 is an Edson EM533 product, and the powder drag reducer is FR-pd (partially hydrolyzed polyacrylamide, molecular weight 1500 ten thousand, Wawton chemical Co., Ltd., Sichuan) as shown in tables 1, 2, and 3 below:
1) stability of
Test method 1 (centrifugation): placing 40ml of a thickening agent sample in a 50ml centrifuge tube with a plug, centrifuging for 1 hour under the condition of 3000r/min, recording the height of supernatant, and calculating the proportion of supernatant in the total liquid volume (namely the liquid-separating degree) of the supernatant;
test method 2 (standing): the thickener samples prepared in examples 1 to 5 and comparative examples 1 to 6 were allowed to stand at a constant temperature of 25 ℃ for 30 days, respectively, and the appearance of the thickener sample was observed and the bulk viscosity of the sample was measured (using a six-speed rotational viscometer, rotation speed 100 r/min).
2) Solubility in water
The test method comprises the following steps: respectively adding 500ml of deionized water into a 1000ml beaker, manually stirring and respectively adding 0.5ml of thickening agent samples, recording the viscosity-rising time after the thickening agent is added (the viscosity-rising phenomenon can be obviously sensed during stirring, and a glass rod can be drawn), and observing whether the samples are completely dissolved.
3) Tackifying and salt resistance
The test method comprises the following steps: stirring simulated saline water at 600r/min, adding thickener sample (0.1%, 0.2%, 0.4% by weight), testing viscosity 2min after adding thickener, and measuring with rheometer for 170s-1Lower viscosity;
the simulated saline formula comprises: according to the weight percentage, 1 percent of sodium chloride, 0.2 percent of potassium chloride, 0.05 percent of calcium chloride and 0.01 percent of magnesium chloride.
4) Resistance reduction rate
The test method comprises the following steps: the drag reduction rate is tested according to the standard NB/T14003.2-2016 part 2 of shale gas fracturing fluid: the performance index of the resistance reducing agent and the testing method are carried out by the method specified in the specification, and the mass fraction of the thickening agent is 0.1 percent.
5) Core damage rate
The test method comprises the following steps: the core damage rate is carried out by adopting the method specified in the standard SY/T5107-2016 water-based fracturing fluid performance evaluation method, and the mass fraction of the thickening agent is 0.1 percent.
TABLE 1 thickener conventional Performance test results
Note: (1) severely delaminated samples fail to test bulk viscosity; (2) and (4) carrying out solubility evaluation on the seriously layered sample after uniformly stirring.
TABLE 2 thickening agent thickening Performance test results in simulated brine
| Sample (I) | 0.1% add viscosity (mPa.s) | 0.2% add viscosity (mPa.s) | 0.4% add viscosity (mPa.s) |
| Sample 1 | 2.737 | 6.463 | 12.12 |
| Sample 2 | 4.097 | 7.642 | 14.25 |
| Sample 3 | 3.562 | 7.173 | 13.26 |
| Sample No. 4 | 3.880 | 7.304 | 13.86 |
| Sample No. 5 | 3.281 | 6.755 | 12.82 |
| FR-WH | 1.46 | 2.729 | 6.143 |
| EM533 | 1.51 | 3.022 | 7.305 |
TABLE 3 core injury comparison of multifunctional viscosifier with conventional oil-based emulsion viscosifier
The comparative examples 1 to 6 have poor stability and no field application value, so that the tackifying performance test and the rock core damage test are not carried out.
As can be seen from the test results in tables 1 to 3, the multifunctional thickener provided by the invention adopts the special dispersant and the special suspending agent to form a super-dispersion system, so that the liquid separation degree in the stability test can reach a very low level, and the problem of unstable dispersion system of other products adopting water-soluble dispersion media is well solved; the product of the invention has lower bulk viscosity and is convenient for field use.
The multifunctional thickening agent provided by the invention has obvious technical advantages in the aspects of viscosity increasing, salt resistance, resistance reduction, low damage and the like, and the good on-line viscosity-changing salt-resistant characteristic of the multifunctional thickening agent is suitable for on-site multistage viscosity-changing sand fracturing operation. Compared with the conventional oil-based emulsion thickening agent, the multifunctional thickening agent of the invention has the advantages of greatly shortened viscosity-raising time, higher viscosity in saline water and far better salt resistance. The multifunctional thickening agent has the obvious effect that the damage rate of the rock core of the multifunctional thickening agent is obviously lower than that of the conventional oil-based emulsion and conventional powder, and belongs to a clean thickening agent product.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The multifunctional thickening agent is characterized by comprising the following raw materials in parts by weight: 30-50 parts of water-soluble thickening agent, 45-55 parts of acetone glycerol, 3-5 parts of D-limonene and 1-2 parts of suspending agent.
2. The multifunctional thickening agent as claimed in claim 1, wherein the raw materials comprise the following components in parts by weight: 30-43 parts of water-soluble thickening agent, 50-55 parts of acetone condensed glycerol, 4-5 parts of D-limonene and 1.5-2 parts of suspending agent;
further, the raw materials comprise the following components in parts by weight: 43 parts of water-soluble thickening agent, 50 parts of acetone condensed glycerol, 5 parts of D-limonene and 2 parts of suspending agent.
3. The multifunctional thickening agent according to claim 1 or 2, wherein the suspending agent is SDS-modified bentonite, and the raw materials of the SDS-modified bentonite comprise the following components in parts by weight: 0.5-1.5 parts of sodium carbonate, 95-105 parts of water, 1-3 parts of sodium dodecyl sulfate and 10-11 parts of bentonite;
further, the SDS modified bentonite comprises the following raw materials in parts by weight: 1.0-1.5 parts of sodium carbonate, 95-99 parts of water, 2-3 parts of sodium dodecyl sulfate and 9-11 parts of bentonite;
further, the SDS modified bentonite comprises the following raw materials in parts by weight: 1.5 parts of sodium carbonate, 95 parts of water, 3 parts of sodium dodecyl sulfate and 11 parts of bentonite.
4. The multifunctional thickener according to any one of claims 1 to 3, wherein the particle size of the suspending agent is 150 mesh or more, preferably 180 mesh or more, and more preferably 200 mesh or more.
5. The multifunctional thickener according to any one of claims 1 to 4, wherein the water-soluble thickener is selected from acrylamide homopolymers and/or acrylamide copolymers and has a molecular weight of 800 to 2500 ten thousand, preferably 1000 to 2000 ten thousand, more preferably 1200 to 1800 ten thousand.
6. The preparation method of the multifunctional thickening agent according to any one of claims 1 to 5, comprising the following steps:
(1) mixing and emulsifying part of the acetone glycerin in the formula amount with a suspending agent to obtain a suspension;
(2) mixing the rest acetone condensed glycerol with a water-soluble thickening agent, and mixing with D-limonene to obtain a polymer dispersion liquid;
(3) mixing the suspension prepared in the step (1) with the polymer dispersion liquid obtained in the step (2).
7. The method for preparing the multifunctional thickening agent according to claim 6, wherein in the step (1), the partial acetone ketal is 5-20%, preferably 8-12%, preferably 8-10%, and more preferably 8% of the total usage amount of the formula.
8. The preparation method of the multifunctional thickening agent according to claim 6, wherein in the step (1), the emulsification condition is 50-70 ℃ for 20-60 min, preferably 55-65 ℃ for 25-35 min, preferably 55-60 ℃ for 30-35 min, and more preferably 55 ℃ for 35 min.
9. The method for preparing the multifunctional thickening agent according to claim 6, wherein the mixing with the D-limonene is performed by adding the D-limonene to the mixture of the acetone condensed glycerol and the water-soluble thickening agent in batches; further, the D-limonene is added in batches within 20-50 min, preferably within 30-40 min, preferably within 30-35 min, and more preferably within 30 min.
10. The preparation method of the multifunctional thickening agent according to any one of claims 6 to 9, further comprising the steps of preparing a suspending agent SDS modified bentonite:
a. mixing water and sodium carbonate, then mixing with sodium dodecyl sulfate and bentonite, and carrying out ultrasonic treatment for 2-5 h at 50-70 ℃ under the condition of 30-50 KHz to obtain a modified bentonite semi-finished product I; preferably, ultrasonic treatment is carried out for 2.5-3.5 h under the conditions of 55-65 ℃ and 35-45 KHz; preferably, the ultrasonic treatment is carried out for 3.0-3.5 h under the conditions of 55-60 ℃ and 35-40 KHz; more preferably, ultrasonic treatment is carried out for 3.5h under the conditions of 55 ℃ and 35 KHz;
b. filtering and drying the modified bentonite semi-finished product I to obtain a modified bentonite semi-finished product II;
c. and grinding the modified bentonite semi-finished product II and sieving the ground product II with a 150-200-mesh sieve, preferably sieving the ground product II with a 180-200-mesh sieve, and more preferably sieving the ground product II with a 200-mesh sieve.
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