CN112062929A - Temporary plugging material and preparation method thereof - Google Patents
Temporary plugging material and preparation method thereof Download PDFInfo
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- CN112062929A CN112062929A CN202010971144.7A CN202010971144A CN112062929A CN 112062929 A CN112062929 A CN 112062929A CN 202010971144 A CN202010971144 A CN 202010971144A CN 112062929 A CN112062929 A CN 112062929A
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Abstract
The invention provides a temporary plugging material and a preparation method thereof, wherein the preparation method comprises the following steps: stirring oxalic acid, polyethylene glycol, a main catalyst and a cocatalyst for reaction for 1-3h under the protection of 100-150 ℃ inert gas, and then stirring for reaction for 2-4h under the vacuum condition of 150-180 ℃ absolute pressure of 50-200Pa to obtain a polyester polyol material; stirring diisocyanate and poly (diethylene glycol adipate) glycol for reaction for 1-2 hours at 60-70 ℃ under the vacuum condition with the absolute pressure of 10-20KPa to obtain a low-temperature temporary plugging prepolymer material; and (3) carrying out reactive extrusion granulation on the polyester polyol material and the low-temperature temporary plugging prepolymer material at the temperature of 150-170 ℃ to obtain the polyester polyol. The temporary plugging material can effectively solve the problems that the existing temporary plugging agent is easy to be sticky at the initial stage of water contact and has poor low-temperature degradation performance.
Description
Technical Field
The invention belongs to the technical field of plugging materials, and particularly relates to a temporary plugging material and a preparation method thereof.
Background
The traditional polyester material and the low-temperature temporary plugging material both have the problems of non-degradability or poor degradability, but in the fields of oil and gas exploitation and the like (for example, as temporary plugging agents), the material is often required to provide higher mechanical strength in a short period, so that pores and cracks of a rock stratum can be effectively plugged, and then the material can be quickly degraded.
Common degradable materials such as polylactic acid (PLA), polyglycolic acid (PGA) and the like can basically meet the degradation requirement of the temporary plugging agent at the temperature of more than 100 ℃, but the degradation speed of the PLA or the PGA is quite slow at a low-temperature reservoir layer such as 40-80 ℃, and the requirement of basic degradation within 3d cannot be met. In addition, PLA and PGA are both rigid materials, and when used as temporary plugging agents, a large amount of flexible temporary plugging materials such as polyacrylic acid are often required to be matched for effective plugging. While materials such as polyacrylic acid have certain solubility properties, they cannot be effectively dissolved in some gas wells or ground seams due to water shortage.
Oxalic acid has strong acidity, and ester bonds formed by oxalic acid esterification have the characteristics of easy hydrolysis and easy breakage. The polymer obtained by using oxalate as a dibasic acid source and matching with dihydric alcohol through ester exchange reaction polycondensation has good low-temperature water degradation performance, but in the existing method for preparing oxalate by using oxalic acid, the reaction time is long, the production efficiency is low, and the method is not suitable for industrial production because a solid-phase polycondensation technology is used. In addition, the produced by-product is an alcohol monomer, so that the method has higher flammable and explosive risks.
Polyethylene glycol (PEG) is a hydroxyl terminated polyether obtained by ring opening polymerization of ethylene oxide, and has excellent water solubility. PEG is often used in the field of polymerization synthesis as a hydrophilic monomer incorporated into a polymerization system.
Boric acid is a weak acid and can also be used as a dehydrating agent in the field of organic synthesis. Boric acid ester formed by esterifying boric acid and alcohols has poor stability and can immediately hydrolyze when meeting water or water vapor.
The oxalic acid and the dihydric alcohol can also be used for synthesizing the polyester, ester bonds of the polyester are very easy to hydrolyze or pyrolyze and break, but the oxalic acid is easy to decompose by heating and the polyester has poor thermal stability, so that the polyoxalic acid dihydric alcohol ester with high molecular weight and high mechanical property is difficult to obtain actually.
In view of the fact that oil and gas resources in China are not abundant, the well temperature of more and more oil and gas wells is reduced after being exploited, and the oil and gas yield is reduced, secondary fracturing development needs to be carried out on low-temperature old wells by adopting a fracturing technology, but the fracturing technology often needs to use a temporary plugging agent. In the prior art, a rigid temporary plugging agent and expanded particles are compounded, the rigid temporary plugging agent is firstly bridged and enriched to form a first plugging layer, and then the expanded particles form a compact plugging layer, but the implementation difficulty is high in the actual operation process. Typical water-soluble expanded particles can be soft and difficult to bridge and enrich. However, if the temporary plugging agent has a structure with soft outside and hard inside, the bridging performance and the plugging strength can be considered at the same time. Although materials such as gelatin and bone glue can be dissolved in water at low temperature, and granules at the initial stage of dissolution also have the characteristics of soft outside and hard inside, and some materials are used as low-temperature temporary plugging agents, the surfaces of the materials immediately start to be sticky and dissolved when the materials enter water, so that serious temporary plugging agents are not yet put down to a preset underground position and then adhere to the well wall, a large amount of waste of the temporary plugging agents is caused, and construction risks are caused.
Therefore, a temporary plugging material having good low-temperature water degradation performance, not being sticky at the initial stage of water contact, and high efficiency is required.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a temporary plugging material and a preparation method thereof, and the temporary plugging material can effectively solve the problems that the existing temporary plugging agent is easy to be sticky at the initial stage of water contact and has poor low-temperature degradation performance.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a temporary plugging material comprises the following steps:
(1) stirring oxalic acid, polyethylene glycol, a main catalyst and a cocatalyst for reaction for 1-3h under the protection of 100-150 ℃ inert gas, and then stirring for reaction for 2-4h under the vacuum condition of 150-180 ℃ absolute pressure of 50-200Pa to obtain a polyester polyol material;
(2) stirring diisocyanate and poly (diethylene glycol adipate) glycol for reaction for 1-2 hours at 60-70 ℃ under the vacuum condition with the absolute pressure of 10-20KPa to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) carrying out reactive extrusion granulation on the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) at the temperature of 150-.
The beneficial effect that above-mentioned scheme produced does: the main chain of the plugging material prepared by the invention contains a large amount of polyethylene glycol chain segments, so that the plugging material has good hydrophilicity, can show the characteristics of softness outside and hardness inside after absorbing water, and has higher plugging strength; oxalic acid and polyethylene glycol react under the catalytic action of a main catalyst and a cocatalyst under the protection of inert gas, so that oxygen radicals can be prevented from participating in the reaction, a polyester polyol comonomer is finally formed, an oxalate bond easy to break is formed in the main chain of the polyester polyol comonomer, the material can be rapidly broken in a low-temperature water environment, the purpose of degradation is achieved, water-soluble polyethylene glycol, adipic acid, diethylene glycol and other non-degradable substances are formed after degradation, and the environment is prevented from being polluted.
Further, in the step (1), the main catalyst and the cocatalyst are stirred and reacted for 2 hours under the protection of 125 ℃ inert gas, and then stirred and reacted for 3 hours under the vacuum condition of 165 ℃ and 150Pa absolute pressure.
Further, the molar ratio of oxalic acid to polyethylene glycol in the step (1) is 100:101-100: 105.
The beneficial effect that above-mentioned scheme produced does: after the oxalic acid and the polyethylene glycol are added according to the proportion, the oxalic acid and the polyethylene glycol can fully react to form a polyester polyol material, so that the number of oxalate bonds in the material is increased, and the dissolving speed under a low-temperature water environment is further increased.
Further, in the step (1), the dosage of the main catalyst is 0.1-1% of the mass of the polyethylene glycol, and the dosage of the cocatalyst is 0.5-1% of the mass of the polyethylene glycol.
Further, in the step (1), the main catalyst is at least one of antimony trioxide, stannous chloride and stannous octoate, and the auxiliary catalyst is boric acid.
In the scheme, the main catalyst is an ester exchange reaction catalyst, and the molecular weight is increased by continuously removing water molecules through ester exchange reaction in a high-temperature and high-vacuum environment. As the polycondensation reaction of the diol and the diacid, the chain extension mechanism is the transesterification reaction rather than the esterification reaction. The catalyst promoter boric acid is a dehydrating agent and is also an esterification reaction catalyst, and the chain growth reaction is promoted through the dehydration esterification reaction. In the application, chain growth is mainly realized through ester exchange reaction, but as the esterification reaction is the first step of realizing the chain growth through the ester exchange reaction, for oxalic acid which is organic acid with extremely poor thermal temperature property, if the esterification reaction can not be realized at the first time to form oxalate, the oxalate can be decomposed by heat, the monomer ratio is influenced, and the growth of a molecular chain is inhibited, so that boric acid ester is formed by using a promoter boric acid to perform the esterification reaction on the oxalic acid, and the oxalic acid is prevented from being decomposed by heat; when the formed boric acid ester is in water, the boric acid ester can be quickly hydrolyzed to release boric acid. The boric acid does not affect the strength of the material in a short period, but can promote the hydrolysis reaction of ester bonds, thereby improving the degradation speed of the material and simultaneously not affecting the temporary plugging performance of the material.
Further, the mass ratio of the cocatalyst to the main catalyst in the step (1) is 5:1-1: 1.
Further, the molar ratio of the poly (diethylene glycol adipate) glycol to the diisocyanate in the step (2) is 1:1.1-1: 1.3.
The beneficial effect that above-mentioned scheme produced does: after the poly diethylene glycol adipate glycol and the diisocyanate are added according to the proportion, the poly diethylene glycol adipate glycol and the diisocyanate fully react to form a poly diethylene glycol adipate prepolymer, the prepolymer is of a structure that the middle is poly diethylene glycol adipate and the two ends are provided with NCO active groups, and the NCO active groups can react with hydroxyl groups, so that the hydrolysis speed of a poly diethylene glycol adipate chain segment is moderate, and the hydrophilicity is moderate. Without the poly (diethylene glycol adipate) component, the material can rapidly absorb water and expand, so that the dissolution speed is too high, and the strength is too low.
Further, in the step (2), diisocyanate and poly (diethylene glycol adipate) glycol are stirred and react for 1-2 hours at 66 ℃ under the vacuum condition of the absolute pressure of 15KPa, so that a low-temperature temporary blocking prepolymer material is obtained.
Further, the number average molecular weight of the polyethylene glycol in the step (1) is 2000-6000, and the number average molecular weight of the poly (diethylene glycol adipate) glycol in the step (2) is 1000-3000.
In the scheme, the phase separation is serious due to the overlarge number average molecular weight, the mechanical property of the material is obviously reduced, and the elasticity of the material is reduced. If the number average molecular weight is too small, the material may show a tendency to be close to a uniform material, or even phase separation does not occur, resulting in a decrease in the water absorption property of the material and difficulty in showing the characteristics of softness at the outside and hardness at the inside after swelling.
Further, the diisocyanate in the step (2) is at least one of hexamethylene-1, 6-diisocyanate, toluene diisocyanate, diphenylmethylene diisocyanate and isophorone diisocyanate.
Further, the mass ratio of the polyester polyol material to the low-temperature temporary plugging prepolymer material in the step (3) is 3:1-5: 1.
The beneficial effect that above-mentioned scheme produced does: the polyester polyol material and the low-temperature temporary plugging prepolymer material are uniformly mixed according to a proper mass ratio, so that the degradation speed can be increased on the basis of ensuring the plugging strength, the plugging strength and the degradation speed of the plugging material can meet the use requirement, and if the proportion of one material is too high or too low, the plugging strength is not enough or the degradation speed is too low.
Further, in step (3), reactive extrusion granulation was performed at 160 ℃.
The beneficial effects brought by the invention are as follows:
1. according to the temporary plugging material provided by the invention, oxalic acid is introduced as a comonomer, and an easily-broken oxalate bond is formed in a polymer main chain, so that the material can be quickly broken in a low-temperature water environment, and the quick dissolution is realized.
2. The temporary plugging material has the characteristic of high strength, and the main chain of the temporary plugging material contains a polyethylene glycol chain segment with large molecular weight, so that the temporary plugging material has good hydrophilicity and can show the characteristics of softness outside and hardness inside after absorbing water, so that a formed filter cake has higher plugging strength; in addition, water-soluble biodegradable monomers such as polyethylene glycol, adipic acid, diethylene glycol and the like are formed after the temporary plugging material is degraded, so that the environmental protection performance of the material is improved.
3. The temporary plugging material has the characteristic of no stickiness when entering water at low temperature, is convenient to go into a well, and particles are not easy to adhere to the wall of the well in the process of going into the well.
4. The temporary plugging material has excellent hot processing performance and good thermoplasticity, and can be extruded and granulated by a double-screw extruder, so that the preparation efficiency is improved.
Drawings
FIG. 1 is a LXD-X1 well low-temperature temporary plugging diversion fracturing construction curve.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
A temporary plugging material is prepared by the following steps:
(1) putting 10mol of oxalic acid, 10.1mol of polyethylene glycol (number average molecular weight 2000), 20.2g of antimony trioxide and 101g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under nitrogen protection and normal pressure at 100 ℃, then heating to 180 ℃, keeping the absolute pressure of 200Pa, and stirring and reacting for 4h in vacuum to obtain a polyester polyol material;
(2) putting 11mol of hexamethylene-1, 6-diisocyanate into a glass kettle with a stirrer, starting the stirrer, heating to 60 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 1000), keeping the absolute pressure of 10Kpa, and stirring in vacuum for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 3:1, performing reactive extrusion at 160 ℃, and then granulating to obtain the low-temperature temporary plugging material containing the easily-broken chemical bonds.
Example 2
A temporary plugging material is prepared by the following steps:
(1) putting 5mol of oxalic acid, 5.25mol of polyethylene glycol (with the number average molecular weight of 4000), 210g of antimony trioxide and 101g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under the protection of nitrogen and normal pressure at the temperature of 100 ℃, then heating to 150 ℃, keeping the absolute pressure of 50Pa, and stirring and reacting for 2h in vacuum to obtain a polyester polyol material;
(2) putting 13mol of toluene diisocyanate into a glass kettle with a stirrer, starting the stirrer, heating to 60 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 1000), keeping the absolute pressure of 10Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 5:1, performing reactive extrusion at the temperature of 150 ℃, and then granulating to obtain the low-temperature temporary plugging material containing the easily-broken chemical bonds.
Example 3
A temporary plugging material is prepared by the following steps:
(1) putting 4mol of oxalic acid, 4.06mol of polyethylene glycol (number average molecular weight 6000), 50g of antimony trioxide, 50g of stannous chloride and 243.6g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under nitrogen protection and normal pressure at 140 ℃, then heating to 170 ℃, keeping the absolute pressure of 110Pa, and stirring and reacting for 3h under vacuum to obtain a polyester polyol material;
(2) putting 3.6mol of diphenyl methylene diisocyanate into a glass kettle with a stirrer, starting the stirrer, heating to 65 ℃, adding 3mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 3000), keeping the absolute pressure of 10Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 3:1, performing reactive extrusion at the temperature of 150 ℃, and then granulating to obtain the low-temperature temporary plugging material containing the easily-broken chemical bonds.
Example 4
A temporary plugging material is prepared by the following steps:
(1) putting 7mol of oxalic acid, 7.1mol of polyethylene glycol (with the number average molecular weight of 3000), 21g of antimony acetate, 42g of stannous octoate and 200g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under the conditions of nitrogen protection and normal pressure at 150 ℃, then heating to 160 ℃, keeping the absolute pressure of 100Pa, and stirring and reacting for 4h in vacuum to obtain a polyester polyol material;
(2) putting 11mol of isophorone diisocyanate into a glass kettle with a stirrer, starting the stirrer, heating to 70 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 2000), keeping the absolute pressure of 20Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 4:1, performing reactive extrusion at the temperature of 150 ℃, and then granulating to obtain the low-temperature temporary plugging material containing the easily-broken chemical bonds.
Example 5
A temporary plugging material is prepared by the following steps:
(1) putting 10mol of oxalic acid, 10.5mol of polyethylene glycol (number average molecular weight 2000), 42g of stannous octoate and 180g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under nitrogen protection and normal pressure at 120 ℃, then heating to 165 ℃, keeping the absolute pressure of 80Pa, and stirring and reacting for 3h in vacuum to obtain a polyester polyol material;
(2) putting 6mol of hexamethylene-1, 6-diisocyanate and 6mol of diphenylmethylene diisocyanate which are measured into a glass kettle with a stirrer, starting the stirrer, heating to 60 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 2000), keeping the absolute pressure of 15Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 4:1, performing reactive extrusion at the temperature of 150 ℃, and then granulating to obtain the low-temperature temporary plugging material containing the easily-broken chemical bonds.
Comparative example 1
A temporary plugging material is prepared by the following steps:
(1) putting 10mol of oxalic acid, 10.5mol of polyethylene glycol (number average molecular weight 2000) and 42g of stannous octoate into a glass kettle with a stirrer together, stirring and reacting for 1h under nitrogen protection and normal pressure at 120 ℃, then heating to 165 ℃, keeping the absolute pressure of 80Pa, and stirring and reacting for 3h in vacuum to obtain a polyester polyol material;
(2) putting 6mol of hexamethylene-1, 6-diisocyanate and 6mol of diphenylmethylene diisocyanate into a glass kettle with a stirrer, starting stirring, heating to 60 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (number average molecular weight 2000), keeping absolute pressure of 15Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 4:1, performing reactive extrusion at the temperature of 150 ℃, and crushing to obtain the low-temperature temporary plugging material containing the easily-breakable chemical bond.
Comparative example 2
A temporary plugging material is prepared by the following steps:
(1) putting 10mol of oxalic acid, 10.5mol of polyethylene glycol (number average molecular weight is 1000), 42g of stannous octoate and 180g of boric acid into a glass kettle with a stirrer, stirring and reacting for 1h under the conditions of nitrogen protection and normal pressure at 120 ℃, then heating to 165 ℃, keeping the absolute pressure of 80Pa, and stirring and reacting for 3h in vacuum to obtain a polyester polyol material;
(2) putting 6mol of hexamethylene-1, 6-diisocyanate and 6mol of diphenylmethylene diisocyanate into a glass kettle with a stirrer, starting stirring, heating to 60 ℃, adding 10mol of poly (diethylene glycol adipate) glycol (with the number average molecular weight of 1000), keeping the absolute pressure of 15Kpa, and carrying out vacuum stirring reaction for 1h to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) injecting the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) into a double-screw extruder by using a gear pump according to the mass ratio of 4:1, performing reactive extrusion at the temperature of 150 ℃, and crushing to obtain the low-temperature temporary plugging material containing the easily-breakable chemical bond in the comparative example.
A temporary plugging material is prepared by the following steps:
and putting 10mol of oxalic acid, 10.5mol of ethylene glycol and 42g of stannous octoate which are measured into a glass kettle with a stirrer together, stirring and reacting for 1h under the conditions of nitrogen protection and normal pressure at 120 ℃, then heating to 165 ℃, keeping the absolute pressure of 80Pa, stirring and reacting for 3h in vacuum, then discharging, cooling and crushing to obtain the material of the comparative example.
Test examples
The temporary plugging materials prepared in examples 1 to 5 and comparative examples 1 to 3 were tested for tensile properties, hydrolytic degradation rate, water absorption, plugging strength and other properties, and the specific test methods are as follows, and the specific test results are shown in table 1.
1. And (3) testing tensile property: the test was carried out on an electronic universal tester model RG1-5 (manufactured by Riger instruments, Inc., Shenzhen, according to the GB/T528-1998 standard). The preparation method of the tensile property test sample strip comprises the following steps: molding a sample strip required by a tensile property test at the injection molding temperature of 140-170 ℃; the injection molding machine used was a KS-8502R injection molding machine, a Kaschin Ke Plastic machinery Co.
2. 50 ℃ hydrolysis degradation rate test: 100ml of water and 4g of a polymer sample to be tested were added to a closed container, the temperature was maintained at 50 ℃ for 24 hours, all the materials were sieved under water using a 200-mesh sieve, and the solids remaining on the sieve were collected, dried and weighed, as undegraded mass. Wherein the polymer sample to be detected is a sample with the particle size of 5-10 meshes screened by a screen.
The degradation rate calculation method comprises the following steps:
3. water absorption test: firstly, crushing a particle sample to be tested into small particles with the diameter of about 1mm for testing, taking 2g of the small particles, pouring the small particles into a beaker filled with 100g of water, soaking the small particles for 30min at the temperature of 25 ℃, then sieving the small particles by a 200-mesh sieve, and weighing solids on the sieve, wherein the weight is the mass after water absorption.
The water absorption test method comprises the following steps:
4. testing the plugging strength: firstly, a particle sample to be tested is crushed into small particles for testing with the diameter of about 1mm, and then the small particles for testing are filled in a simulated crack by adopting a core fluidity tester (Jiangsu Hua' an scientific research instrument Co., Ltd.) to test the plugging strength of the small particles. The core model is a sand filling pipe: the diameter is 5cm, and the length is 20 cm; the test set temperature is 50 ℃; using simulated bottom brine at a depth of less than 1cm3Displacing the core at a flow rate of/min, and collecting the discharged liquid by using a balance; the lower layer of the sand filling pipe is made of quartz sand for fracturing of 20-40 meshes, the upper layer is made of small particles for testing with the thickness of 11mm, the small particles are tightly screwed and then loaded into a core fluidity tester, simulated formation saline water is slowly injected,and testing the plugging strength.
Table 1: performance statistics table
Note: "/" indicates no test or failed test
From the experimental data, it can be seen that the low-temperature temporary plugging material containing the easily breakable chemical bond in the embodiments 1 to 5 has high tensile strength, good color, excellent low-temperature water degradation performance, water absorption expansibility and higher plugging strength, and the performance of each aspect of the low-temperature temporary plugging material is superior to that of the plugging material in the comparative examples 1 to 3, so that the low-temperature temporary plugging material is very suitable for being used as a low-temperature temporary plugging agent for oil and gas exploitation. In addition, the low-temperature temporary plugging material containing the easily-broken chemical bond also has good processing performance and good thermoplasticity, and can be processed into various products by injection molding.
Comparing the plugging material in comparative example 1 with the plugging material in the example, it can be seen that oxalic acid is easy to decompose at high temperature without the help of a catalyst, thereby affecting the monomer ratio and appearance color, causing the prepared polyethylene oxalate glycol ester polyol to have too low molecular weight, further causing low strength, low melt viscosity, inability of injection molding processing, and slow degradation speed.
Comparing the plugging material in comparative example 2 with the plugging material in the examples, it can be seen that the polyethylene glycol has a smaller number average molecular weight of 1000, which causes the prepared material to have insignificant phase separation and poor elasticity, thereby affecting the dissolution rate and plugging strength.
Comparing the plugging material in comparative example 3 with the plugging material in the examples, it can be seen that the strength of the prepared polyethylene glycol oxalate is low, the viscosity is also low, the plugging strength is poor, and the degradation speed is slow because no cocatalyst, diisocyanate, and poly (diethylene glycol adipate) glycol are used.
Case (2): temporary plugging case for low temperature well
The LXD-X1 well is used for compacting a sandstone reservoir, the vertical depth is about 1600m, the formation temperature is about 45 ℃, and the formation pressure is about 14.5 MPa; perforationThe well section 1610m to 1613m is injected by a phi 73 oil pipe for construction, and the discharge capacity is 3.2 to 3.6m3Min, oil pressure of 21.1-51.7 MPa and liquid volume of 360m3Sand amount 35m3. The intermediate adopts a novel low-temperature rapid self-degradation crack temporary plugging diverting agent to carry out interlayer temporary plugging diverting construction, and the delivery volume of the agent is 1.0m3The dosage of the low-temperature temporary plugging agent is 200kg, under the condition that the construction discharge capacity before and after temporary plugging is the same, the construction pressure before temporary plugging is 45.9MPa, the construction pressure after temporary plugging is 51.7MPa, and the pressure amplitude before and after temporary plugging is 5.8MPa, so that the interlayer stress difference can be effectively overcome, and the crack temporary plugging steering effect is obvious.
Claims (10)
1. The preparation method of the temporary plugging material is characterized by comprising the following steps of:
(1) stirring oxalic acid, polyethylene glycol, a main catalyst and a cocatalyst for reaction for 1-3h under the protection of 100-150 ℃ inert gas, and then stirring for reaction for 2-4h under the vacuum condition of 150-180 ℃ absolute pressure of 50-200Pa to obtain a polyester polyol material;
(2) stirring diisocyanate and poly (diethylene glycol adipate) glycol for reaction for 1-2 hours at 60-70 ℃ under the vacuum condition with the absolute pressure of 10-20KPa to obtain a low-temperature temporary plugging prepolymer material;
(3) and (3) carrying out reactive extrusion granulation on the polyester polyol material in the step (1) and the low-temperature temporary plugging prepolymer material in the step (2) at the temperature of 150-.
2. The method for preparing a temporary plugging material according to claim 1, wherein the molar ratio of oxalic acid to polyethylene glycol in step (1) is 100:101-100: 105.
3. A method for preparing a temporary plugging material according to claim 1, wherein the amount of the main catalyst used in step (1) is 0.1-1% by mass of the polyethylene glycol, and the amount of the cocatalyst is 0.5-1% by mass of the polyethylene glycol.
4. A method for preparing a temporary plugging material according to claim 1 or 3, wherein in the step (1), the main catalyst is at least one of antimony trioxide, stannous chloride and stannous octoate, and the auxiliary catalyst is boric acid.
5. A method for preparing a temporary plugging material according to claim 1, wherein the mass ratio of the cocatalyst to the main catalyst in the step (1) is 5:1 to 1:1.
6. A process for preparing a temporary blocking material according to claim 1, wherein the molar ratio of the polyethylene glycol adipate diol to the diisocyanate in step (2) is 1:1.1 to 1: 1.3.
7. The method for preparing a temporary plugging material as claimed in claim 1, wherein the number average molecular weight of the polyethylene glycol in the step (1) is 2000-6000, and the number average molecular weight of the polyethylene glycol adipate glycol in the step (2) is 1000-3000.
8. A process for producing a temporary blocking material according to claim 1, wherein the diisocyanate in the step (2) is at least one of hexamethylene-1, 6-diisocyanate, tolylene diisocyanate, diphenylmethylene diisocyanate and isophorone diisocyanate.
9. A method for preparing a temporary plugging material according to claim 1, wherein the mass ratio of the polyester polyol material to the low-temperature temporary plugging prepolymer material in the step (3) is 3:1 to 5: 1.
10. A temporary plugging material produced by the production method according to any one of claims 1 to 9.
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