CN107502321B - Novel foam drilling fluid system and preparation method thereof - Google Patents
Novel foam drilling fluid system and preparation method thereof Download PDFInfo
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- CN107502321B CN107502321B CN201710546975.8A CN201710546975A CN107502321B CN 107502321 B CN107502321 B CN 107502321B CN 201710546975 A CN201710546975 A CN 201710546975A CN 107502321 B CN107502321 B CN 107502321B
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- C09K8/02—Well-drilling compositions
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Abstract
The invention relates to a novel foam drilling fluid system and a preparation method thereof. The novel foam drilling fluid system is developed on the basis of the developed novel foaming foam stabilizer. The novel foaming foam stabilizer has the advantages of novel structure and excellent performance, a large amount of foam can be generated by a small amount of foaming foam stabilizer, and the half-life period of the foam can reach more than 3 times of that of the conventional foaming agent. The single foaming foam stabilizer can achieve the compounding effect of various foaming agents and has less addition. When the addition amount of the foaming foam stabilizer is very small, the half-life period of the novel foam drilling fluid system developed based on the novel foaming foam stabilizer can reach 7.1d, and is obviously superior to that of the foam drilling fluid prepared by a conventional foaming agent. The novel foam drilling fluid system has good performance, can resist the temperature of 120 ℃, resists 10% of salt, resists 12% of debris pollution, has the mud shale recovery rate of more than 90%, has the linear expansion reduction rate of more than 80%, has no leakage in 80/120-mesh sandstone, has the leakage of less than 1.2ml in 40/80-mesh sandstone, and can effectively meet the requirements of site construction.
Description
Technical Field
The invention belongs to the technical field of petroleum and natural gas drilling, and relates to a novel foam drilling fluid system and a preparation method thereof.
Background
Compared with the conventional drilling fluid, the foam drilling fluid has low density, can improve the drilling speed of drilling machinery, can solve the problems of stratum leakage and the like, and has low filtration loss, low reservoir damage and very wide field application prospect. The foam drilling fluid is generally prepared from a foaming agent, a foam stabilizer, a tackifier, a fluid loss additive, a weighting agent and other treatment agents, wherein the foaming agent is one of core treatment agents and is a treatment agent which enables foam to be easily generated and has certain stability after being generated. The main types of the foaming agent comprise anionic type, cationic type, amphoteric type and nonionic type, wherein the anionic type foaming agent has high foaming performance, wide application, good use effect, moderate price and wide source. The prior common foam drilling fluid is developed by optimizing the prior foaming agent and compounding with other treating agents, and has the advantages of large addition of the treating agents, poor foam stability, high cost and short half-life period. At present, the research on the foaming agent mainly focuses on the optimization and compounding by using the existing surfactant, but the research on the molecular structure design of the foaming agent is relatively less, and many foaming agents are designed and synthesized aiming at the aspects of oil resistance, temperature resistance and the like, are not designed from the aspects of improving the foaming quality such as increasing the foaming amount and prolonging the half-life period, and are higher in addition amount, so that the cost is not reduced.
Patent CN 201610821642.7 discloses a foam drilling fluid, which comprises a first foaming agent, a second foaming agent, inorganic fibers and water, wherein the mass percentage of the first foaming agent is 2% -4%, the mass percentage of the second foaming agent is 1% -2%, the dosage of the first foaming agent is twice that of the second foaming agent, the mass percentage of the inorganic fibers is 1% -3%, and the balance is water. Dispersing inorganic fibers in deionized water at normal temperature and normal pressure for prehydration for 8-12 h, then adding a first foaming agent and a second foaming agent, uniformly stirring at 60-80 ℃, and foaming at the rotating speed of 5000-8000 r/min for 3-5 min to obtain the foam drilling fluid. The half-life period of the foam drilling fluid can reach 80min, the foam drilling fluid is very low, the consumption of a foaming agent is high, and the cost is high.
Disclosure of Invention
In order to overcome the defects of the prior art, on the basis of the developed novel foaming foam stabilizer, the invention provides a novel foam drilling fluid system and a preparation method thereof, the half-life of the novel foam drilling fluid system can reach 7.1 days when the addition amount of the foaming foam stabilizer is very small, and the half-life of the novel foam drilling fluid system is obviously superior to that of the foam drilling fluid prepared by the conventional foaming agent. The novel foam drilling fluid system has good performance, can resist the temperature of 120 ℃, resists 10% of salt, resists 12% of debris pollution, has the mud shale recovery rate of more than 90%, has the linear expansion reduction rate of more than 80%, has no leakage in 80/120-mesh sandstone, has the leakage of less than 1.2ml in 40/80-mesh sandstone, and can effectively meet the requirements of site construction.
The invention provides the following technical scheme:
a novel foam drilling fluid system comprises the following components:
0.2 wt% of foaming foam stabilizer;
0.2 wt% of a foam stabilizer;
0.8 wt% tackifier;
0.2 wt% fluid loss additive;
0.1 wt% -1 wt% weighting agent;
the balance of water; wherein the mass percent of each component is based on water.
In the above embodiment, the foam stabilizer preferably has a formula shown in formula (i):
in any of the above embodiments, preferably, the foam stabilizer is carboxymethyl cellulose (CMC), and the appearance: white, odorless, tasteless, hygroscopic particles; the water content is less than or equal to 7 percent; the pH value is 7.0-8.0; the fineness (screen residue of a screen hole of 0.9 mm) is less than or equal to 8 percent.
Preferably in any of the above embodiments, the foam stabiliser is a biopolymer XC, appearance: a light yellow powder; the water content is less than or equal to 8 percent; the pH value is 7.0-8.0; the fineness (screen residue of a screen hole of 0.9 mm) is less than or equal to 5 percent.
In any of the above embodiments, preferably, the viscosifier is a polyanionic cellulose (PAC) based compound having an appearance: a white powder; the water content is less than or equal to 6 percent; the pH value is 7.0-8.0; intrinsic viscosity 100 ml/g: not less than 9; the fineness (screen residue of a screen hole of 0.9 mm) is less than or equal to 6 percent.
Preferably in any of the above embodiments, the viscosifier is hydroxyethyl cellulose (HEC) with an appearance: a white powder; the water content is less than or equal to 6 percent; the pH value is 7.0-8.0; intrinsic viscosity 100 ml/g: not less than 8; the fineness (screen residue of a screen hole of 0.9 mm) is less than or equal to 8 percent.
In any of the above embodiments, preferably, the fluid loss additive is lignite resin (SPNH) or hydroxypropyl starch (HPS); lignite resin, appearance: black brown powder; the water content is less than or equal to 10 percent; water insoluble matter is less than or equal to 10 percent; the high-temperature and high-pressure filtration loss is less than or equal to 20 ml; hydroxypropyl starch, appearance: a white powder; the water content is less than or equal to 11 percent; water insoluble matter is less than or equal to 9 percent; the high-temperature and high-pressure filtration loss is less than or equal to 18 ml.
Preferably in any of the above embodiments, the weighting agent is barite or calcium carbonate; barite, appearance: a white powder; the purity is more than or equal to 98 percent; density: 3.9g/cm3～4.2g/cm3(ii) a The fineness (screen residue of a screen hole of 0.9 mm) is less than or equal to 1 percent; calcium carbonate, appearance: a white powder; the purity is more than or equal to 98 percent; density: 2.7g/cm3～2.9g/cm3(ii) a Acid insoluble substance is less than or equal to 1 percent; the fineness (screen residue of 0.9mm screen mesh) is less than or equal to 1 percent.
In any of the above embodiments, it is preferable that in the preparation method of the foam stabilizer, the catalyst BF is added with isododecanol3Reacting with epoxy ether to generate alcohol ether under the action of an ether solution, and then reacting with chlorosulfonic acid and sodium hydroxide in sequence to generate the foaming stabilizer.
In any of the above embodiments, preferably, the preparation method of the foaming foam stabilizer comprises the following steps:
(1) mixing and stirring 1, 3-propylene glycol, epichlorohydrin and tetrabutylammonium hydrogen sulfate; dripping 50% NaOH aqueous solution, and continuously stirring; separating out an organic phase after liquid separation, adding ethanol into the organic phase, carrying out hot filtration to remove inorganic salt, and distilling to remove ethanol and epoxy chloropropane to obtain epoxy ether;
(2) slowly dripping cold concentrated sulfuric acid into tetrapropylene, stirring, dripping the obtained mixture into a 50% NaOH aqueous solution, stirring, separating out an organic phase after liquid separation, adding ethanol into the organic phase, carrying out hot filtration to remove inorganic salts, and distilling to remove ethanol and tetrapropylene to obtain isododecanol;
(3) dripping BF into the isododecanol prepared in the step (2)3-diethyl ether solution, stirring, heating, stirringDropwise adding the epoxy ether prepared in the step (1), heating and stirring, neutralizing with a 2% NaOH aqueous solution until the pH value is 7, separating the liquid, separating an organic phase, and distilling to remove the isododecanol and the epoxy ether to obtain alcohol ether;
(4) and (3) dropwise adding chlorosulfonic acid into the alcohol ether prepared in the step (3) under stirring, removing HCl gas, stirring, neutralizing with a 2% NaOH ethanol solution until the pH value is 7, adding ethanol, carrying out hot filtration to remove inorganic salts, and distilling to remove ethanol to obtain the foaming stabilizer.
In any of the above schemes, preferably, in the step (1), the using ratio of the 1, 3-propylene glycol, the epichlorohydrin and the tetrabutylammonium hydrogen sulfate is 70 ml-100 ml: 150 ml-250 ml: 5g to 15 g.
In any of the above schemes, preferably, in step (1), the 1, 3-propanediol, the epichlorohydrin and the tetrabutylammonium hydrogen sulfate are stirred at 35 ℃ to 45 ℃.
In any of the above embodiments, preferably, in the step (1), the volume ratio of the 50% NaOH aqueous solution to the 1, 3-propanediol is 500ml to 650 ml: 70ml to 100 ml.
In any of the above schemes, preferably, in the step (1), after the 50% NaOH aqueous solution is added, the stirring is continued for 2 to 3 hours at 55 to 65 ℃.
In any of the above embodiments, preferably, in the step (2), the volume ratio of the amount of the tetrapropylene to the 1, 3-propanediol is 200ml to 300 ml: 70ml to 100 ml.
In any of the above schemes, preferably, in the step (2), the cold concentrated sulfuric acid is slowly added dropwise at 0 ℃, and the volume ratio of the dosage of the cold concentrated sulfuric acid to the dosage of the 1, 3-propylene glycol is 60 ml-70 ml: 70ml to 100 ml.
In any of the above schemes, preferably, in the step (2), the cold concentrated sulfuric acid is added and stirred for 2 to 3 hours.
In any of the above embodiments, preferably, in the step (2), the volume ratio of the 50% NaOH aqueous solution to the 1, 3-propanediol is 150ml to 250 ml: 70ml to 100 ml.
In any of the above embodiments, preferably, in the step (2), the mixture of tetrapropylene and the cold concentrated sulfuric acid is added dropwise to the 50% NaOH aqueous solution at a temperature of 10 ℃ to 20 ℃ and stirred for 2 hours to 3 hours.
In any of the above embodiments, it is preferable that, in the step (3), the BF is3-the volume ratio of the amount of the diethyl ether solution to the 1, 3-propanediol is 5ml to 10 ml: 70ml to 100 ml.
In any of the above embodiments, it is preferable that BF is dropped into the product isododecanol of the step (2) in the step (3)3Stirring the ether solution and raising the temperature to 35-45 ℃ for a moment.
In any of the schemes, preferably, in the step (3), the epoxy ether product obtained in the step (1) is added dropwise under the condition of stirring, the temperature is raised to 75-85 ℃ after the dripping is finished, and the stirring is carried out for 4-6 h.
In any of the above schemes, preferably, in the step (4), the volume ratio of the dosage of the chlorosulfonic acid to the dosage of the 1, 3-propanediol is 30ml to 40 ml: 70ml to 100 ml.
In any of the above schemes, preferably, in the step (4), chlorosulfonic acid is slowly dropped into the alcohol ether product of the step (3) at a temperature of 5 ℃ to 15 ℃ while stirring, HCl gas is removed by using a tail gas recovery device, and the mixture is stirred for 3h to 4 h.
The invention also provides a preparation method of the novel foam drilling fluid system, which comprises the following steps:
(1) adding water into a stirring cup, and starting a stirrer to stir at 10000 r/min-12000 r/min;
(2) adding the foam stabilizer, continuing to stir to fully dissolve the foam stabilizer, then adding the tackifier, continuing to stir to fully dissolve the tackifier, then adding the filtrate reducer, continuing to stir to fully dissolve the filtrate reducer, then adding the weighting agent, continuing to stir to fully disperse the weighting agent uniformly, finally adding the foaming foam stabilizer, and continuing to stir for 1-3 min to prepare the foam drilling fluid system.
In the above aspect, it is preferable that the method includes the steps of:
(1) adding water into a stirring cup, and starting a stirrer to stir at 11000 r/min;
(2) adding the foam stabilizer, continuing to stir to fully dissolve the foam stabilizer, then adding the tackifier, continuing to stir to fully dissolve the tackifier, then adding the filtrate reducer, continuing to stir to fully dissolve the filtrate reducer, then adding the weighting agent, continuing to stir to fully disperse the weighting agent uniformly, finally adding the foaming foam stabilizer, and continuing to stir for 2min to prepare the foam drilling fluid system.
In order to improve the field application effect of the foam drilling fluid, the invention starts from the relationship between the foaming performance and the molecular structure of a core treating agent foaming agent of the foam drilling fluid, optimizes the structure of the foaming agent, improves the foaming amount and the half-life period, reduces the use concentration, develops a novel molecular structure foaming agent with high foaming amount and good foam stability at lower concentration, and is compounded with an optimized foam stabilizer, a tackifier, a filtrate reducer and a weighting agent on the basis of developing the foam stabilizer to construct a novel foam drilling fluid system, wherein the half-life period can be as long as 7.1d when the addition amount of the foam stabilizer is very small, and is obviously superior to the half-life period of the foam drilling fluid prepared by the conventional foaming agent. The novel foam drilling fluid system has good performance, can resist the temperature of 120 ℃, resists 10% of salt, resists 12% of debris pollution, has the mud shale recovery rate of more than 90%, has the linear expansion reduction rate of more than 80%, has no leakage in 80/120-mesh sandstone, has the leakage of less than 1.2ml in 40/80-mesh sandstone, and can effectively meet the requirements of site construction.
Drawings
FIG. 1 is an infrared spectrum of a preferred embodiment of a novel foam drilling fluid system in accordance with the present invention;
FIG. 2 is a mass spectrum of the embodiment of FIG. 1 of a novel foam drilling fluid system according to the present invention;
FIG. 3 is a graph of surface tension versus concentration of the aqueous foam stabilizer solution of the embodiment of FIG. 1 of a novel foam drilling fluid system according to the present invention;
FIG. 4 is a graph showing the foaming performance of the embodiment of the foam stabilizer of FIG. 1 in accordance with the present invention for a novel foam drilling fluid system;
FIG. 5 is a graph showing the salt resistance of the 0.2% foam stabilizer of the embodiment of FIG. 1 of a novel foam drilling fluid system according to the present invention.
Detailed Description
In order to further illustrate the technical features of the present invention, the present invention is described in detail with reference to the following embodiments. The embodiments are given by way of illustration only and not by way of limitation, and any insubstantial modifications, based on the present disclosure, may be made by those skilled in the art without departing from the scope of the present disclosure.
Example 1:
a novel foam drilling fluid system comprises the following components:
0.2 wt% of foaming foam stabilizer;
0.2 wt% carboxymethyl cellulose;
0.8 wt% of high viscosity polyanionic cellulose PAC-HV;
0.2 wt% lignite resin;
0.1 wt% barite;
the balance of water; wherein the mass percent of each component is based on water.
The preparation method of the foam drilling fluid system comprises the following steps:
(1) adding 100ml of water into a stirring cup, and starting a stirrer to stir at 11000 r/min;
(2) adding 0.2 wt% of carboxymethyl cellulose, continuing to stir to fully dissolve, adding 0.8 wt% of high-viscosity polyanionic cellulose PAC-HV, continuing to stir to fully dissolve, adding 0.2 wt% of lignite resin, continuing to stir to fully dissolve, adding 0.1 wt% of barite, continuing to stir to fully disperse uniformly, adding 0.2 wt% of foaming foam stabilizer, and continuing to stir for 2min to prepare the foam drilling fluid system. The mass percentage of each component is based on water.
In this embodiment, the formula of the foaming foam stabilizer is shown as formula (i):
example 2:
a novel foam drilling fluid system comprises the following components:
0.2 wt% of foaming foam stabilizer;
0.2 wt% biopolymer XC;
0.8 wt% hydroxyethyl cellulose;
0.2 wt% hydroxypropyl starch;
0.1 wt% calcium carbonate;
the balance of water; wherein the mass percent of each component is based on water.
The preparation method of the foam drilling fluid system comprises the following steps:
(1) adding 100ml of water into a stirring cup, and starting a stirrer to stir at 11000 r/min;
(2) adding 0.2 wt% of biopolymer XC, continuing to stir to fully dissolve, adding 0.8 wt% of hydroxyethyl cellulose, continuing to stir to fully dissolve, adding 0.2 wt% of hydroxypropyl starch, continuing to stir to fully dissolve, adding 0.1 wt% of calcium carbonate, continuing to stir to fully disperse uniformly, adding 0.2 wt% of foaming stabilizer, and continuing to stir for 2min to prepare the foam drilling fluid system. The mass percentage of each component is based on water.
In this embodiment, the formula of the foaming foam stabilizer is shown as formula (i):
example 3:
a novel foam drilling fluid system comprises the following components:
0.2 wt% of foaming foam stabilizer;
0.2 wt% carboxymethyl cellulose;
0.8 wt% hydroxyethyl cellulose;
0.2 wt% hydroxypropyl starch;
0.1 wt% barite;
the balance of water; wherein the mass percent of each component is based on water.
The preparation method of the foam drilling fluid system comprises the following steps:
(1) adding 100ml of water into a stirring cup, and starting a stirrer to stir at 11000 r/min;
(2) adding 0.2 wt% of carboxymethyl cellulose, continuing to stir to fully dissolve, adding 0.8 wt% of hydroxyethyl cellulose, continuing to stir to fully dissolve, adding 0.2 wt% of hydroxypropyl starch, continuing to stir to fully dissolve, adding 0.1 wt% of barite, continuing to stir to fully disperse uniformly, adding 0.2 wt% of foaming foam stabilizer, and continuing to stir for 2min to prepare the foam drilling fluid system. The mass percentage of each component is based on water.
In this embodiment, the formula of the foaming foam stabilizer is shown as formula (i):
in order to clearly show the invention effect of the foam drilling fluid system, performance evaluation including half-life period, rheological property, temperature resistance, salt resistance, debris pollution resistance, inhibition property and plugging property is performed on the foam drilling fluid system of the invention in the embodiment 1-3.
Test example 1: novel foam drilling fluid performance evaluation
1. Half life and rheological Properties
The prepared foam drilling fluid of examples 1-3 was immediately poured into a 1000ml graduated cylinder while a stopwatch was started and t was recorded1/2-half life of the eluent. The prepared foam drilling fluids of examples 1-3 were additionally taken and the AV-apparent viscosity of the foam drilling fluids was measured on a six-speed rotational viscometer. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the half-life period of the foam drilling fluid reaches 7.1d, the foam drilling fluid is obviously superior to the half-life period of the foam drilling fluid prepared by the conventional foaming agent, and the rheological property is good.
TABLE 1 basic properties and rheological Properties of foam drilling fluids
2. Temperature resistance
And (3) putting the prepared foam drilling fluid of the examples 1-3 into an aging tank, putting the aging tank into a high-temperature roller furnace, rolling at the constant temperature of 120 ℃ for 16 hours, taking out the foam drilling fluid, cooling to the room temperature, stirring at a high speed for 2min, and measuring the basic performance and rheological property of the foam drilling fluid. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the half-life period and the viscosity of the foam drilling fluid are slightly reduced after rolling aging at 120 ℃ for 16 hours, while the half-life period of the comparative example with a large amount of foaming agent is greatly reduced, and the temperature resistance of the foam drilling fluid reaches 120 ℃.
TABLE 2 temperature resistance of foam drilling fluids
3. Salt resistance
And (3) adding NaCl with different mass fractions into the prepared foam drilling fluid of the examples 1-3, and measuring the basic performance and rheological property of the foam drilling fluid after stirring at a high speed for 2 min. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the half-life period and the viscosity of the foam drilling fluid slowly increase along with the increase of the mass fraction of NaCl, when the mass fraction of NaCl is more than 4%, the half-life period and the viscosity slowly decrease, while the half-life period of a comparative example with more foaming agent is reduced quickly, and the salt pollution resistance of the foam drilling fluid reaches 10%.
TABLE 3 salt resistance of foam drilling fluids
4. Resistance to debris contamination
And adding rock debris with different mass fractions into the prepared foam drilling fluid of the examples 1-3, and measuring the basic performance and rheological property of the foam drilling fluid after stirring at a high speed for 2 min. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the half-life period of the foam drilling fluid is slowly reduced and the viscosity is slowly improved along with the increase of the mass fraction of rock debris, while the half-life period of a comparative example with a large amount of foaming agent is quickly reduced, and the rock debris pollution resistance of the foam drilling fluid reaches 12%.
TABLE 4 debris contamination resistance of foam drilling fluids
5. Inhibition performance
Taking a certain amount of drill cuttings with the mesh number of 6-10 meshes, and drying at 105 ℃; 350ml of the foam drilling fluid of examples 1 to 3 and 50.00g of the dried drill cuttings are added into an aging tank and aged for 16h at 120 ℃; sieving the aged solution with a 40-mesh sieve, and naturally washing with tap water; the washed drill cuttings were dried at 105 ℃, weighed and the shale recovery was calculated. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention.
Crushing the dried rock debris to obtain rock debris powder, and preparing an evaluation core block (under the pressure of 4MPa, pressing for 5 min); starting the dilatometer, installing the evaluation core block, and pouring the foam drilling fluid of the embodiment 1-3 after zero setting; starting the test, and recording the linear expansion amount (mm) after every 0.5 h; and (5) comparing with clear water, and calculating the linear expansion reduction rate. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the foam drilling fluid has higher mud shale recovery rate and linear expansion reduction rate, while the comparative example with more foaming agent is lower in mud shale recovery rate and linear expansion reduction rate, and the foam drilling fluid has better inhibition performance.
TABLE 5 inhibition performance of foam drilling fluids
6. Plugging performance
200g of sand with different particle sizes (80/120 meshes and 40/80 meshes) is put into a medium-pressure water loss instrument cup, the foam drilling fluid in the embodiment is added, and the leakage of the foam drilling fluid at the room temperature and the pressure of 0.7MPa is measured. While replacing the foaming stabilizer (0.2 wt%) in example 3 with the conventional foaming agent sodium lauryl sulfate (0.5 wt%) as a control example, the properties thereof were evaluated without changing other conditions to illustrate the effects of the present invention. The result shows that when the foaming foam stabilizer is added in a small amount, the foam drilling fluid disclosed by the invention has no leakage in 80/120-mesh sandstone, the leakage in 40/80-mesh sandstone is lower, the leakage of a comparative example with a large amount of foaming agent is higher, and the plugging performance of the foam drilling fluid disclosed by the invention is better.
TABLE 6 plugging Properties of foam drilling fluids
Example 4:
a method for preparing the foam stabilizer of examples 1-3, comprising the steps of:
(1) 85ml of 1, 3-propylene glycol, 200ml of epichlorohydrin and Bu of tetrabutylammonium hydrogen sulfate are added into a three-neck flask4NHSO4(TBAS)8g, stirred at a temperature of 40 ℃; 600ml of 50% NaOH aqueous solution was added dropwise from a constant pressure dropping funnel, and stirring was continued at 60 ℃ for 2.5 hours. Separating the upper organic phase with a separating funnel, adding ethanol, hot filtering to remove inorganic salts, distilling to remove ethanol and ethanolEpoxy chloropropane is adopted to obtain epoxy ether with the yield of 96.7 percent and the purity of 90.8 percent.
(2) 265ml tetrapropylene was added to a three-necked flask, 65ml cold concentrated sulfuric acid was slowly dropped dropwise at 0 ℃ using an isopiestic dropping funnel, and after stirring for 2 hours, the mixture was transferred to the isopiestic dropping funnel, 200ml of a 50% NaOH aqueous solution was added to the three-necked flask, and the mixture was dropped at 10 ℃ and stirred for 2 hours. Separating the upper organic phase with separating funnel, adding alcohol, hot filtering to eliminate inorganic salt, distilling to eliminate alcohol and tetrapropylene to obtain isododecanol in 82.6% yield and 92.2% purity.
(3) Adding the product of the step (2) isododecanol into a three-neck flask, and dripping 10ml of BF3And (2) heating the solution to 40 ℃ with stirring, dropwise adding the epoxy ether product obtained in the step (1) under stirring, heating the solution to 80 ℃ after the dropwise addition, stirring for 5 hours, neutralizing the solution with a 2% NaOH aqueous solution until the pH value is 7, separating an upper organic phase by using a separating funnel, and distilling to remove isododecanol and the epoxy ether to obtain alcohol ether with the yield of 81.3% and the purity of 89.9%.
(4) And (3) adding the alcohol ether product obtained in the step (3) into a three-neck flask, dropwise and slowly adding 30ml of chlorosulfonic acid at the temperature of 10 ℃ under the stirring state, removing HCl gas by using a tail gas recovery device, stirring for 3h, neutralizing with 2% NaOH ethanol solution until the pH value is 7, adding ethanol, thermally filtering to remove inorganic salts, and distilling to remove the ethanol to obtain the final product, namely the foaming foam stabilizer, wherein the yield is 90.1% and the purity is 93.7%.
Infrared spectroscopic analysis of the foam stabilizer prepared in this example was carried out by infrared spectroscopic analysis, see FIG. 1.
The infrared spectrum analysis result is 2854cm as shown in figure 1-1、2922cm-11468cm as C-H stretching vibration absorption peak-1Flexural vibration absorption Peak of C-H, 1206cm-1And 1251cm-1Is the telescopic vibration absorption peak of C-O connected with sulfate ester, 1080cm-1The stretching vibration absorption peaks of ether bonds C-O correspond to functional groups of the molecular structure of the foaming foam stabilizer, and the successful synthesis of the designed foaming foam stabilizer is shown.
Mass Spectrometry, the foam stabilizer prepared in this example was analyzed by mass spectrometry, see FIG. 2.
The mass spectrometry result is shown in FIG. 2, the molecular weight of the foam stabilizer of this example is 764, and 2 Na ions are removed+The molecular weight of the anionic fragment is 718, the anionic fragment has 2 negative charges, the mass-to-charge ratio is 359, the anionic fragment is consistent with a peak 359.14849 on a mass spectrogram, and the peak 265.14790 is obtained by removing 1 Na from sodium dodecyl sulfate impurity+The latter anionic fragment formed, indicating the successful synthesis of the designed foam stabilizer.
The reaction equation of the preparation method of the novel foaming foam stabilizer is as follows:
example 5:
the difference between this example and example 4 is:
the preparation method of the foaming foam stabilizer comprises the following steps:
(1) 70ml of 1, 3-propylene glycol, 150ml of epichlorohydrin and Bu of tetrabutylammonium hydrogen sulfate are added into a three-neck flask4NHSO4(TBAS)5g, stirred at a temperature of 35 ℃; 500ml of 50% NaOH aqueous solution was added dropwise from a constant pressure dropping funnel, and stirring was continued at 55 ℃ for 2 hours. Separating the upper organic phase by using a separating funnel, adding ethanol, carrying out hot filtration to remove inorganic salt, and distilling to remove ethanol and epoxy chloropropane to obtain epoxy ether with the yield of 93.0% and the purity of 90.1%.
(2) 200ml of tetrapropylene was added to a three-necked flask, 60ml of cold concentrated sulfuric acid was slowly dropped dropwise at a temperature of 0 ℃ with a constant pressure dropping funnel, and after stirring for 2 hours, the mixture was transferred to the constant pressure dropping funnel, 150ml of a 50% NaOH aqueous solution was added to the three-necked flask, and the mixture was dropped at a temperature of 10 ℃ and stirred for 2 hours. Separating the upper organic phase with separating funnel, adding alcohol, hot filtering to eliminate inorganic salt, distilling to eliminate alcohol and tetrapropylene to obtain isododecanol in 80.8% yield and 91.0% purity.
(3) Adding the product isododecanol obtained in the step (2) into a three-neck flask, and dripping 5ml of BF3An ether solution, the temperature is raised to 35 ℃ for a moment by stirring, the epoxy ether which is the product of the step (1) is added dropwise under the stirring condition,after the completion of the dropping, the temperature was raised to 75 ℃, the mixture was stirred for 4 hours, the mixture was neutralized with a 2% aqueous solution of NaOH until the pH became 7, an upper organic phase was separated with a separatory funnel, and isododecanol and epoxy ether were distilled off to obtain an alcohol ether in a yield of 80.4% and a purity of 88.1%.
(4) And (3) adding alcohol ether of the product in the step (3) into a three-neck flask, dropwise and slowly adding 30ml of chlorosulfonic acid at the temperature of 5 ℃ under the stirring condition, removing HCl gas by using a tail gas recovery device, stirring for 3h, neutralizing pH (7) by using a 2% NaOH ethanol solution, adding ethanol, thermally filtering to remove inorganic salts, and distilling to remove the ethanol to obtain a final product, namely the foaming foam stabilizer, wherein the yield is 88.9% and the purity is 90.5%.
Example 6:
the difference between this example and example 5 is:
the preparation method of the foaming foam stabilizer comprises the following steps:
(1) 100ml of 1, 3-propylene glycol, 250ml of epichlorohydrin and Bu of tetrabutylammonium hydrogen sulfate are added into a three-neck flask4NHSO4(TBAS)15g, stirred at 45 ℃; 650ml of 50% aqueous NaOH solution were added dropwise from a constant pressure dropping funnel and stirring was continued at 65 ℃ for 3 h. Separating the upper organic phase by using a separating funnel, adding ethanol, carrying out hot filtration to remove inorganic salt, and distilling to remove ethanol and epoxy chloropropane to obtain epoxy ether with the yield of 95.5% and the purity of 94.2%.
(2) 300ml of tetrapropylene was charged into a three-necked flask, 70ml of cold concentrated sulfuric acid was slowly dropped dropwise at 0 ℃ with a constant pressure dropping funnel, and after stirring for 3 hours, the mixture was transferred to the constant pressure dropping funnel, 250ml of a 50% NaOH aqueous solution was added into the three-necked flask, and the mixture was dropped at 20 ℃ and stirred for 3 hours. Separating the upper organic phase with separating funnel, adding alcohol, hot filtering to eliminate inorganic salt, distilling to eliminate alcohol and tetrapropylene to obtain isododecanol in 83.6% yield and 90.8% purity.
(3) Adding the product of the step (2) isododecanol into a three-neck flask, and dripping 10ml of BF3Heating to 45 ℃ with stirring, dropwise adding the epoxy ether product obtained in the step (1) under stirring, heating to 85 ℃ after dropwise adding, stirring for 6h, neutralizing with 2% NaOH aqueous solution until the pH value is 7, and separating the upper organic layer with a separating funnelAnd distilling to remove the isododecanol and the epoxy ether to obtain alcohol ether with the yield of 82.4% and the purity of 90.2%.
(4) And (3) adding alcohol ether of the product in the step (3) into a three-neck flask, dropwise and slowly adding 40ml of chlorosulfonic acid at the temperature of 15 ℃ under the stirring condition, removing HCl gas by using a tail gas recovery device, stirring for 4h, neutralizing with 2% NaOH ethanol solution to pH 7, adding ethanol, thermally filtering to remove inorganic salts, and distilling to remove the ethanol to obtain a final product, namely the foaming foam stabilizer, wherein the yield is 89.3% and the purity is 92.8%.
Test example 2: evaluation of foam stabilizer Properties prepared in example 4
1. Surface tension
The surface tension of the foam stabilizer aqueous solutions at different concentrations was tested, and as shown in FIG. 3, the surface tension gradually decreased with increasing foam stabilizer concentration, and decreased to 20.40mN · m when the concentration was increased to 0.2%-1And the surface tension is reduced by 71.82 percent compared with that of pure water, which shows that the foaming foam stabilizer of the embodiment 4 of the invention has stronger surface activity and is beneficial to improving the foaming performance.
2. Foaming Property test
Foaming properties are primarily referred to as foaming capacity and foam stability. Foaming volume V0Reflecting the foaming capacity and the half-life t of the solution1/2Reflecting the foam stability. The foaming volume and half-life period of the novel foaming stabilizer with different concentrations are tested, and the results are shown in fig. 4, and it can be seen that the foaming volume of the foaming stabilizer reaches 610ml when the mass fraction of the foaming stabilizer is 0.2%, and the half-life period reaches 1440s, the mass fraction is continuously improved, and the foaming performance is slightly increased but is not obvious, which indicates that the foaming stabilizer developed in example 4 of the present invention has a good foaming effect at low concentration, and has a large foaming amount and good foam stability.
The foaming performance of the foaming stabilizer is evaluated by respectively testing the foaming volume and half life of 0.2 percent of the foaming stabilizer, 0.5 percent of the common foaming agent and gemini surfactant under the same foaming condition. The test method refers to the evaluation program of the foaming agent for SY/T5350-2009 drilling fluid, the test results are shown in Table 1, and the comparison shows that the novel surfactant foaming stabilizer in the embodiment 4 of the invention can achieve a higher foaming effect at a lower concentration, has a higher foaming volume and half-life period, and improves the half-life period by more than 3 times.
TABLE 8 testing of the foaming Properties of the different blowing agents
3. Salt resistance
The salt resistance of the foaming foam stabilizer mainly refers to the NaCl pollution resistance. NaCl with different mass fractions is added into the foaming foam stabilizer solution with the mass fraction of 0.2% to evaluate the salt resistance of the foaming foam stabilizer solution, and the results are shown in figure 5, when the NaCl addition is within 3%, the foaming volume and the half-life period of the novel foaming foam stabilizer are slightly reduced, and the reduction range is relatively gentle, which indicates that the foaming foam stabilizer developed in the embodiment 4 of the invention has better salt resistance.
Claims (25)
1. A foam drilling fluid system is characterized by comprising the following components:
0.2 wt% of a foam stabilizer having the formula (I):
0.2 wt% of a foam stabilizer;
0.8 wt% tackifier;
0.2 wt% fluid loss additive;
0.1 wt% -1 wt% weighting agent;
the balance of water; wherein the mass percent of each component is based on water.
2. The foam drilling fluid system of claim 1, wherein: the foam stabilizer is carboxymethyl cellulose, and has the appearance: white, odorless, tasteless, hygroscopic particles; the water content is less than or equal to 7 percent; the pH value is 7.0-8.0; the screen residue of 0.9mm screen holes is less than or equal to 8 percent.
3. The foam drilling fluid system of claim 1, wherein: the foam stabilizer is a biopolymer XC, and the appearance is as follows: a light yellow powder; the water content is less than or equal to 8 percent; the pH value is 7.0-8.0; the screen residue of 0.9mm of screen holes is less than or equal to 5 percent.
4. The foam drilling fluid system of claim 1, wherein: the tackifier is a polyanionic cellulose compound, and the appearance is as follows: a white powder; the water content is less than or equal to 6 percent; the pH value is 7.0-8.0; intrinsic viscosity 100 ml/g: not less than 9; the screen residue of 0.9mm screen holes is less than or equal to 6 percent.
5. The foam drilling fluid system of claim 1, wherein: the tackifier is hydroxyethyl cellulose, and the appearance is as follows: a white powder; the water content is less than or equal to 6 percent; the pH value is 7.0-8.0; intrinsic viscosity 100 ml/g: not less than 8; the screen residue of 0.9mm screen holes is less than or equal to 8 percent.
6. The foam drilling fluid system of claim 1, wherein: the fluid loss additive is lignite resin or hydroxypropyl starch; lignite resin, appearance: black brown powder; the water content is less than or equal to 10 percent; water insoluble matter is less than or equal to 10 percent; the high-temperature and high-pressure filtration loss is less than or equal to 20 ml; hydroxypropyl starch, appearance: a white powder; the water content is less than or equal to 11 percent; water insoluble matter is less than or equal to 9 percent; the high-temperature and high-pressure filtration loss is less than or equal to 18 ml.
7. The foam drilling fluid system of claim 1, wherein: the weighting agent is barite or calcium carbonate; barite, appearance: a white powder; the purity is more than or equal to 98 percent; density: 3.9g/cm3～4.2g/cm3(ii) a The screen residue with 0.9mm of screen holes is less than or equal to 1 percent; calcium carbonate, appearance: a white powder; the purity is more than or equal to 98 percent; density: 2.7g/cm3～2.9g/cm3(ii) a Acid insoluble substance is less than or equal to 1 percent; the screen residue of 0.9mm of screen holes is less than or equal to 1 percent.
8. The foam drilling fluid of claim 1The system is characterized in that: the preparation method of the foaming foam stabilizer comprises the step of adding the isododecanol into a catalyst BF3Reacting with epoxy ether to generate alcohol ether under the action of an ether solution, and then reacting with chlorosulfonic acid and sodium hydroxide in sequence to generate the foaming stabilizer.
9. The foam drilling fluid system of claim 8, wherein: the preparation method of the foaming foam stabilizer comprises the following steps:
(1) mixing and stirring 1, 3-propylene glycol, epichlorohydrin and tetrabutylammonium hydrogen sulfate; dripping 50% NaOH aqueous solution, and continuously stirring; separating out an organic phase after liquid separation, adding ethanol into the organic phase, carrying out hot filtration to remove inorganic salt, and distilling to remove ethanol and epoxy chloropropane to obtain epoxy ether;
(2) slowly dripping cold concentrated sulfuric acid into tetrapropylene, stirring, dripping the obtained mixture into a 50% NaOH aqueous solution, stirring, separating out an organic phase after liquid separation, adding ethanol into the organic phase, carrying out hot filtration to remove inorganic salts, and distilling to remove ethanol and tetrapropylene to obtain isododecanol;
(3) dripping BF into the isododecanol prepared in the step (2)3Stirring and heating the ether solution, dropwise adding the epoxy ether prepared in the step (1) under stirring, heating and stirring, neutralizing with a 2% NaOH aqueous solution until the pH value is 7, separating liquid, separating an organic phase, and distilling to remove isododecanol and the epoxy ether to obtain alcohol ether;
(4) and (3) dropwise adding chlorosulfonic acid into the alcohol ether prepared in the step (3) under stirring, removing HCl gas, stirring, neutralizing with a 2% NaOH ethanol solution until the pH value is 7, adding ethanol, carrying out hot filtration to remove inorganic salts, and distilling to remove ethanol to obtain the foaming stabilizer.
10. The foam drilling fluid system of claim 9, wherein: in the step (1), the dosage ratio of 1, 3-propylene glycol, epichlorohydrin to tetrabutylammonium hydrogen sulfate is 70 ml-100 ml: 150 ml-250 ml: 5g to 15 g.
11. The foam drilling fluid system of claim 10, wherein: in the step (1), the 1, 3-propylene glycol, the epichlorohydrin and the tetrabutylammonium hydrogen sulfate are stirred at the temperature of 35-45 ℃.
12. The foam drilling fluid system of claim 11, wherein: in the step (1), the volume ratio of the 50% NaOH aqueous solution to the 1, 3-propylene glycol is 500 ml-650 ml: 70ml to 100 ml.
13. The foam drilling fluid system of claim 12, wherein: in the step (1), the 50 percent NaOH aqueous solution is added, and then the mixture is continuously stirred for 2 to 3 hours at the temperature of between 55 and 65 ℃.
14. The foam drilling fluid system of claim 13, wherein: in the step (2), the volume ratio of the amount of the tetrapropylene to the 1, 3-propylene glycol is 200 ml-300 ml: 70ml to 100 ml.
15. The foam drilling fluid system of claim 14, wherein: in the step (2), the cold concentrated sulfuric acid is slowly dripped dropwise at the temperature of 0 ℃, and the volume ratio of the dosage of the cold concentrated sulfuric acid to the dosage of the 1, 3-propylene glycol is 60-70 ml: 70ml to 100 ml.
16. The foam drilling fluid system of claim 15, wherein: and (3) adding the cold concentrated sulfuric acid into the mixture and stirring the mixture for 2 to 3 hours.
17. The foam drilling fluid system of claim 16, wherein: in the step (2), the volume ratio of the 50% NaOH aqueous solution to the 1, 3-propylene glycol is 150 ml-250 ml: 70ml to 100 ml.
18. The foam drilling fluid system of claim 17, wherein: in the step (2), the mixture of tetrapropylene and cold concentrated sulfuric acid is dripped into the 50 percent NaOH aqueous solution at the temperature of 10-20 ℃ and stirred for 2-3 h.
19. The foam drilling fluid system of claim 18, wherein: in the step (3), the BF3-the volume ratio of the amount of the diethyl ether solution to the 1, 3-propanediol is 5ml to 10 ml: 70ml to 100 ml.
20. The foam drilling fluid system of claim 19, wherein: in the step (3), BF is dropped into the product of the step (2), i.e. isododecanol3Stirring the ether solution and raising the temperature to 35-45 ℃ for a moment.
21. The foam drilling fluid system of claim 20, wherein: in the step (3), the epoxy ether which is the product of the step (1) is added dropwise under the condition of stirring, the temperature is raised to 75-85 ℃ after the dripping is finished, and the stirring is carried out for 4-6 h.
22. The foam drilling fluid system of claim 21, wherein: in the step (4), the volume ratio of the dosage of the chlorosulfonic acid to the dosage of the 1, 3-propylene glycol is 30 ml-40 ml: 70ml to 100 ml.
23. The foam drilling fluid system of claim 22, wherein: in the step (4), the product alcohol ether in the step (3) is stirred, chlorosulfonic acid is dropwise and slowly added at the temperature of 5-15 ℃, a tail gas recovery device is adopted to remove HCl gas, and the stirring is carried out for 3-4 hours.
24. A method of preparing a foamed drilling fluid system according to any one of claims 1 to 23, comprising the steps of:
(1) adding water into a stirring cup, and starting a stirrer to stir at 10000 r/min-12000 r/min;
(2) adding the foam stabilizer, continuing to stir to fully dissolve the foam stabilizer, then adding the tackifier, continuing to stir to fully dissolve the tackifier, then adding the filtrate reducer, continuing to stir to fully dissolve the filtrate reducer, then adding the weighting agent, continuing to stir to fully disperse the weighting agent uniformly, finally adding the foaming foam stabilizer, and continuing to stir for 1-3 min to prepare the foam drilling fluid system.
25. The method of preparing a foamed drilling fluid system according to claim 24, wherein: the method comprises the following steps:
(1) adding water into a stirring cup, and starting a stirrer to stir at 11000 r/min;
(2) adding the foam stabilizer, continuing to stir to fully dissolve the foam stabilizer, then adding the tackifier, continuing to stir to fully dissolve the tackifier, then adding the filtrate reducer, continuing to stir to fully dissolve the filtrate reducer, then adding the weighting agent, continuing to stir to fully disperse the weighting agent uniformly, finally adding the foaming foam stabilizer, and continuing to stir for 2min to prepare the foam drilling fluid system.
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| CN113122200B (en) * | 2019-12-31 | 2022-07-12 | 中石化石油工程技术服务有限公司 | Medium-high temperature hard rubber recyclable foam drilling fluid and preparation method thereof |
| CN113122201B (en) * | 2019-12-31 | 2022-07-29 | 中石化石油工程技术服务有限公司 | High-temperature ebonite recyclable foam drilling fluid and preparation method thereof |
| CN113969147B (en) * | 2020-07-23 | 2022-12-23 | 中石化石油工程技术服务有限公司 | High-temperature protective agent for micro-foam drilling fluid and preparation method thereof |
| CN112457828B (en) * | 2020-12-02 | 2023-01-03 | 中联煤层气有限责任公司 | Use and maintenance method of micro-foam drilling fluid |
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| CN101148579A (en) * | 2007-10-27 | 2008-03-26 | 东营泰尔石油技术有限公司 | High temperature resistant circulating micro-foam drilling fluid or completion fluid |
| CN101314710A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
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| CN101148579A (en) * | 2007-10-27 | 2008-03-26 | 东营泰尔石油技术有限公司 | High temperature resistant circulating micro-foam drilling fluid or completion fluid |
| CN101314710A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
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