CN107502321A - A kind of novel foam drilling fluid system and preparation method thereof - Google Patents
A kind of novel foam drilling fluid system and preparation method thereof Download PDFInfo
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- CN107502321A CN107502321A CN201710546975.8A CN201710546975A CN107502321A CN 107502321 A CN107502321 A CN 107502321A CN 201710546975 A CN201710546975 A CN 201710546975A CN 107502321 A CN107502321 A CN 107502321A
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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
- C09K8/02—Well-drilling compositions
- C09K8/38—Gaseous or foamed well-drilling compositions
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Abstract
The present invention relates to a kind of novel foam drilling fluid system and preparation method thereof.The novel foam drilling fluid system is developed on the basis of the new foaming foam stabilizer of development.The new foaming foam stabilizer has the advantages of novel structure, function admirable, and a small amount of foam stabilizer that bubbles can produce a large amount of foams, and half foam life period is up to more than 3 times of conventional blister agent.The effect that single foaming foam stabilizer compounds with regard to that can reach existing a variety of foaming agents, and dosage is less.Based on the novel foam drilling fluid system of the new foaming foam stabilizer development, when the foam stabilizer dosage that bubbles is seldom, half-life period is 7.1 d, hence it is evident that the half-life period for the foam drilling fluid prepared better than conventional blister agent.Novel foam drilling fluid system has good performance, can 120 DEG C of temperature resistance, salt resistance 10%, anti- landwaste pollution 12%, the mud shale rate of recovery more than 90%, line swell increment reduced rate more than 80%, without leakage in 80/120 mesh sandstone, below the ml of wastage 1.2 in 40/80 mesh sandstone, can effectively meet site operation requirement.
Description
Technical field
The invention belongs to oil and gas drilling technology field, is related to a kind of novel foam drilling fluid system and its preparation
Method.
Background technology
Foam drilling fluid and conventional drilling liquid phase ratio, drilling fluid density is low, can improve drilling machinery drilling speed, can solve stratum
The problems such as leakage, and filter loss is low, and reservoir damage is low, and field application prospect is quite varied.Foam drilling fluid is typically by bubbling
The inorganic agents such as agent, foam stabilizer, tackifier, fluid loss additive, weighting agent are prepared, and wherein foaming agent is one of core processing agent,
It is to make foam be easy to produce and have the inorganic agent of certain stability after generation.Foaming agent main Types include anionic,
Cationic, amphoteric, nonionic, wherein anionic foaming agent frothing capacity are high, and using wide, using effect is good, price
Moderate and source is wide.Conventional foam drilling fluid is that existing foaming agent is carried out preferably at present, and compounds and grind with other inorganic agents
System, inorganic agent dosage is more, and foam stability is poor, and cost is high, half-life short.The research of foaming agent is concentrated mainly on utilization at present
Existing surfactant, carry out preferably with compounding, and the research in terms of foaming agent Molecular Design is fewer, and a lot
It is to be directed to oil resistivity, temperature resistance of foaming agent etc. to be designed synthesis, does not increase foaming such as from raising frothing quality
Amount, the angle of extension half-life period are designed, and dosage is higher, is unfavorable for reducing cost.
Patent CN 201610821642.7 discloses a kind of foam drilling fluid, including the first foaming agent, the second foaming agent,
Inorfil and water, the mass percent of the first foaming agent are 2%~4%, the mass percent of the second foaming agent for 1%~
2%, and the first foaming agent consumption is the second foaming agent consumption twice, the mass percent of inorfil is 1%~3%, surplus
For water.Under normal temperature and pressure conditionses, inorfil is scattered in deionized water and carries out prehydration processing 8h~12h, is then added again
Enter the first foaming agent and the second foaming agent, 60 DEG C~80 DEG C stir, and are bubbled with 5000r/min~8000r/min rotating speed
3min~5min, produce foam drilling fluid.The foam drilling fluid half-life period is up to 80min, very low, and its foaming agent consumption
Higher, cost is high.
The content of the invention
For overcome the deficiencies in the prior art, on the basis of the new foaming foam stabilizer of development, the present invention provides a kind of
Novel foam drilling fluid system and preparation method thereof, the novel foam wellbore fluid tie up to foaming foam stabilizer dosage it is seldom when, half
The phase of declining is 7.1d, hence it is evident that the half-life period for the foam drilling fluid prepared better than conventional blister agent.Novel foam wellbore fluid
System has good performance, can 120 DEG C of temperature resistance, salt resistance 10%, anti-landwaste pollutes 12%, the mud shale rate of recovery more than 90%, line
Swell increment reduced rate more than 80%, without leakage in 80/120 mesh sandstone, below the wastage 1.2ml in 40/80 mesh sandstone, energy
Effectively meet site operation requirement.
The invention provides following technical scheme：
A kind of novel foam drilling fluid system, including following component：
0.2wt% foaming foam stabilizers；
0.2wt% foam stabilizers；
0.8wt% tackifier；
0.2wt% fluid loss additives；
0.1wt%~1wt% weighting agents；
Surplus is water；Wherein the benchmark of the mass percent of each component is water.
In such scheme preferably, shown in the molecular formula such as formula (I) of the foaming foam stabilizer：
In any of the above-described scheme preferably, the foam stabilizer is carboxymethyl cellulose (CMC), outward appearance：White, nothing
It is smelly, tasteless, have hygroscopicity particle；Moisture≤7%；PH=7.0~8.0；Fineness (sieve aperture 0.9mm is tailed over)≤8%.
In any of the above-described scheme preferably, the foam stabilizer is biopolymer XC, outward appearance：Pale yellow powder；Water
Divide≤8%；PH=7.0~8.0；Fineness (sieve aperture 0.9mm is tailed over)≤5%.
In any of the above-described scheme preferably, the tackifier are polyanion cellulose (PAC) class compounds, outside
See：White powder；Moisture≤6%；PH=7.0~8.0；Inherent viscosity 100ml/g：≥9；Fineness (sieve aperture 0.9mm is tailed over)≤
6%.
In any of the above-described scheme preferably, the tackifier are hydroxyethyl cellulose (HEC), outward appearance：White powder；
Moisture≤6%；PH=7.0~8.0；Inherent viscosity 100ml/g：≥8；Fineness (sieve aperture 0.9mm is tailed over)≤8%.
In any of the above-described scheme preferably, the fluid loss additive is walchowite (SPNH) or hydroxypropul starch
(HPS)；Walchowite, outward appearance：Dark brown powder；Moisture≤10%；Water-insoluble≤10%；High temperature and high pre ssure filtration≤
20ml；Hydroxypropul starch, outward appearance：White powder；Moisture≤11%；Water-insoluble≤9%；High temperature and high pre ssure filtration≤18ml.
In any of the above-described scheme preferably, the weighting agent is barite or calcium carbonate；Barite, outward appearance：White
Powder；Purity >=98%；Density：3.9g/cm3~4.2g/cm3；Fineness (sieve aperture 0.9mm is tailed over)≤1%；Calcium carbonate, outward appearance：
White powder；Purity >=98%；Density：2.7g/cm3~2.9g/cm3；Acid non-soluble substance≤1%；Fineness (sieve aperture 0.9mm is tailed over)
≤ 1%.
In any of the above-described scheme preferably, the preparation method of the foaming foam stabilizer, different lauryl alcohol is in catalyst
BF3The effect of-diethyl ether solution is lower and ether epoxy reaction generates alcohol ether, is then reacted successively with chlorosulfonic acid, sodium hydroxide described in generation
Bubble foam stabilizer.
In any of the above-described scheme preferably, the preparation method of the foaming foam stabilizer, including following steps：
(1) 1,3- propane diols, epoxychloropropane and 4-butyl ammonium hydrogen sulfate are mixed；It is water-soluble to instill 50%NaOH
Liquid, continue to stir；Organic phase is separated after liquid separation, ethanol is added in organic phase, heat filtering removes inorganic salts, ethanol is distilled off
And epoxychloropropane, obtain ether epoxy；
(2) cold concentrated sulfuric acid stirring is slowly added dropwise in polypropylene tetramer, it is water-soluble that obtained mixture is added dropwise to 50%NaOH
In liquid, stirring, separate organic phase after liquid separation, add ethanol in organic phase, heat filtering removes inorganic salts, be distilled off ethanol and
Polypropylene tetramer, obtain different lauryl alcohol；
(3) BF is instilled in different lauryl alcohol prepared by step (2)3- diethyl ether solution, stirring, heating, is added dropwise step under agitation
Suddenly the ether epoxy that prepared by (1), heating stirring, is neutralized to pH=7 with the 2%NaOH aqueous solution, organic phase is separated after liquid separation, distillation removes
Different lauryl alcohol and ether epoxy are removed, obtains alcohol ether；
(4) in alcohol ether prepared by step (3), agitation and dropping chlorosulfonic acid, HCl gases, stirring, with 2%NaOH second are removed
Alcoholic solution is neutralized to pH=7, adds ethanol, and heat filtering removes inorganic salts, ethanol is distilled off, obtains the foaming foam stabilizer.
In any of the above-described scheme preferably, in step (1), 1,3-PD, epoxychloropropane and tetrabutyl sulfuric acid
The amount ratio of hydrogen ammonium is 70ml~100ml：150ml~250ml：5g~15g.
In any of the above-described scheme preferably, in step (1), the 1,3-PD, the epoxychloropropane and institute
4-butyl ammonium hydrogen sulfate is stated to stir at 35 DEG C~45 DEG C.
In any of the above-described scheme preferably, in step (1), the 50%NaOH aqueous solution and the 1,3-PD
Dosage volume ratio be 500ml~650ml：70ml~100ml.
In any of the above-described scheme preferably, in step (1), after adding the 50%NaOH aqueous solution, continue 55
DEG C~65 DEG C of stirring 2h~3h.
In any of the above-described scheme preferably, in step (2), the dosage of the polypropylene tetramer and the 1,3-PD
Volume ratio is 200ml~300ml：70ml~100ml.
In any of the above-described scheme preferably, in step (2), the cold concentrated sulfuric acid is slowly added dropwise dropwise at 0 DEG C, described
The dosage volume ratio of the cold concentrated sulfuric acid and the 1,3- propane diols is 60ml~70ml：70ml~100ml.
In any of the above-described scheme preferably, in step (2), 2h~3h is stirred after adding the cold concentrated sulfuric acid.
In any of the above-described scheme preferably, in step (2), the 50%NaOH aqueous solution and the 1,3-PD
Dosage volume ratio be 150ml~250ml：70ml~100ml.
In any of the above-described scheme preferably, in step (2), at a temperature of 10 DEG C~20 DEG C, to the 50%NaOH
The mixture of the polypropylene tetramer and the cold concentrated sulfuric acid is added dropwise in the aqueous solution, stirs 2h~3h.
In any of the above-described scheme preferably, in step (3), the BF3- diethyl ether solution and the 1,3- propane diols
Dosage volume ratio is 5ml~10ml：70ml~100ml.
In any of the above-described scheme preferably, in step (3), BF is instilled in the different lauryl alcohol of step (2) product3- second
Ethereal solution, stirring a moment are warming up to 35 DEG C~45 DEG C.
In any of the above-described scheme preferably, in step (3), step (1) product ring is added dropwise under agitation
Oxygen ether, 75 DEG C~85 DEG C are warming up to after dripping off, stir 4h~6h.
In any of the above-described scheme preferably, in step (4), the dosage body of the chlorosulfonic acid and the 1,3-PD
Product ratio is 30ml~40ml：70ml~100ml.
In any of the above-described scheme preferably, in step (4), step (3) product alcohol ether under agitation, at 5 DEG C
Chlorosulfonic acid is slowly added dropwise dropwise at a temperature of~15 DEG C, HCl gases are removed using device for recovering tail gas, stir 3h~4h.
The present invention also provides the preparation method of described novel foam drilling fluid system, comprises the following steps：
(1) add water in jar, turn on agitator is stirred under the conditions of 10000r/min~12000r/min；
(2) foam stabilizer is added, continuing stirring makes it fully dissolve, and then adds the tackifier, and continuing stirring makes
It fully dissolves, and adds the fluid loss additive, and continuing stirring makes it fully dissolve, and adds the weighting agent, continues to stir
Make its fully dispersed uniform, be eventually adding the foaming foam stabilizer, continue stirring 1min~3min and be prepared into the foam drilling
Liquid system.
In such scheme preferably, comprise the following steps：
(1) add water in jar, turn on agitator is stirred under the conditions of 11000r/min；
(2) foam stabilizer is added, continuing stirring makes it fully dissolve, and then adds the tackifier, and continuing stirring makes
It fully dissolves, and adds the fluid loss additive, and continuing stirring makes it fully dissolve, and adds the weighting agent, continues to stir
Make its fully dispersed uniform, be eventually adding the foaming foam stabilizer, continue stirring 2min and be prepared into the Foam.
In order to improve the foam drilling fluid effect of field application present invention from the core processing agent foaming agent of foam drilling fluid
Frothing capacity and the relation of molecular structure are set out, and optimize foaming agent structure, improve foam number and half-life period, reduce concentration,
A kind of foaming agent for the new molecular architecture that foam number in low concentration is high, foam stability is good is developed, it is steady developing foaming
On the basis of infusion, compounded with preferable foam stabilizer, tackifier, fluid loss additive, weighting agent, build a kind of novel foam and bore
Well liquid system, when the foam stabilizer dosage that bubbles is seldom, half-life period is 7.1d, hence it is evident that the bubble prepared better than conventional blister agent
The half-life period of foam drilling fluid.Novel foam drilling fluid system has good performance, can 120 DEG C of temperature resistance, salt resistance 10%, anti-landwaste
Pollution 12%, the mud shale rate of recovery more than 90%, line swell increment reduced rate more than 80%, without leakage in 80/120 mesh sandstone,
Below the wastage 1.2ml in 40/80 mesh sandstone, it can effectively meet site operation requirement.
Brief description of the drawings
Fig. 1 is the red of foam stabilizer of bubbling according to an a kind of preferred embodiment of novel foam drilling fluid system of the present invention
External spectrum figure；
Fig. 2 is the foaming foam stabilizer according to a kind of embodiment illustrated in fig. 1 of novel foam drilling fluid system of the present invention
Mass spectrogram；
Fig. 3 is the foaming foam stabilizer water according to a kind of embodiment illustrated in fig. 1 of novel foam drilling fluid system of the present invention
The surface tension of solution and the relation of concentration；
Fig. 4 is the foaming foam stabilizer according to a kind of embodiment illustrated in fig. 1 of novel foam drilling fluid system of the present invention
Frothing capacity；
Fig. 5 is the 0.2% foaming foam stabilizing according to a kind of embodiment illustrated in fig. 1 of novel foam drilling fluid system of the present invention
The anti-salt property of agent.
Embodiment
In order to further illustrate the technical characteristic of the present invention, the present invention is explained in detail with reference to specific embodiment
State.Embodiment only to the present invention have the function that it is exemplary, without the effect of any restrictions, those skilled in the art
The modification for any unsubstantiality made on the basis of the present invention, should all belong to protection scope of the present invention.
Embodiment 1：
A kind of novel foam drilling fluid system, including following each component：
0.2wt% foaming foam stabilizers；
0.2wt% carboxymethyl celluloses；
The high adhesive aggregation anionic cellulose PAC-HV of 0.8wt%；
0.2wt% walchowites；
0.1wt% barites；
Surplus is water；Wherein the benchmark of the mass percent of each component is water.
The preparation method of Foam described in the present embodiment, comprises the following steps：
(1) 100ml water is taken to add in jar, turn on agitator is stirred under the conditions of 11000r/min；
(2) 0.2wt% carboxymethyl cellulose is added, continuing stirring makes it fully dissolve, and it is cloudy to add the high adhesive aggregations of 0.8wt%
Ion fiber element PAC-HV, continuing stirring makes it fully dissolve, and adds 0.2wt% walchowites, and continuing stirring makes it fully molten
Solution, 0.1wt% barites are added, continuing stirring makes its fully dispersed uniformly, adds 0.2wt% foaming foam stabilizers, continues to stir
2min is prepared into Foam.The benchmark of the mass percent of above-mentioned each component is water.
In the present embodiment, shown in the molecular formula such as formula (I) of the foaming foam stabilizer：
Embodiment 2：
A kind of novel foam drilling fluid system, including following each component：
0.2wt% foaming foam stabilizers；
0.2wt% biopolymers XC；
0.8wt% hydroxyethyl celluloses；
0.2wt% hydroxypropul starch；
0.1wt% calcium carbonate；
Surplus is water；Wherein the benchmark of the mass percent of each component is water.
The preparation method of Foam described in the present embodiment, comprises the following steps：
(1) 100ml water is taken to add in jar, turn on agitator is stirred under the conditions of 11000r/min；
(2) 0.2wt% biopolymer XC are added, continuing stirring makes it fully dissolve, and adds 0.8wt% hydroxy ethyl fibers
Element, continuing stirring makes it fully dissolve, and adds 0.2wt% hydroxypropul starch, and continuing stirring makes it fully dissolve, and adds
0.1wt% calcium carbonate, continuing stirring makes its fully dispersed uniformly, adds 0.2wt% foaming foam stabilizers, continues to stir 2min preparations
Obtain Foam.The benchmark of the mass percent of above-mentioned each component is water.
In the present embodiment, shown in the molecular formula such as formula (I) of the foaming foam stabilizer：
Embodiment 3：
A kind of novel foam drilling fluid system, including following each component：
0.2wt% foaming foam stabilizers；
0.2wt% carboxymethyl celluloses；
0.8wt% hydroxyethyl celluloses；
0.2wt% hydroxypropul starch；
0.1wt% barites；
Surplus is water；Wherein the benchmark of the mass percent of each component is water.
The preparation method of Foam described in the present embodiment, comprises the following steps：
(1) 100ml water is taken to add in jar, turn on agitator is stirred under the conditions of 11000r/min；
(2) 0.2wt% carboxymethyl celluloses are added, continuing stirring makes it fully dissolve, and adds 0.8wt% hydroxy ethyl fibers
Element, continuing stirring makes it fully dissolve, and adds 0.2wt% hydroxypropul starch, and continuing stirring makes it fully dissolve, and adds
0.1wt% barites, continuing stirring makes its fully dispersed uniformly, adds 0.2wt% foaming foam stabilizers, continues to stir 2min preparations
Obtain Foam.The benchmark of the mass percent of above-mentioned each component is water.
In the present embodiment, shown in the molecular formula such as formula (I) of the foaming foam stabilizer：
In order to clearly illustrate the invention effect of Foam of the present invention, the present invention is to embodiment 1~3
Performance evaluation, including half-life period and rheological property, heat-resisting property, salt resistance and anti-landwaste pollutant performance, rejection, envelope are carried out
Stifled performance.
Test example 1：Novel foam drilling liquid performance evaluating
1. half-life period and rheological property
The embodiment 1-3 prepared foam drilling fluid is poured into 1000ml graduated cylinders immediately, while starts stopwatch, is recorded
t1/2- analysis liquid half-life period.The another foam drilling fluid for taking the embodiment 1-3 prepared, foam drilling is determined on six fast rotation viscometers
The AV- apparent viscosities of well liquid.The foaming foam stabilizer (0.2wt%) in embodiment 3 is replaced with into conventional blister agent dodecane simultaneously
Base sodium sulphate (0.5wt%) is used as reference examples, and other conditions are constant, evaluates its performance to illustrate the effect of the present invention.As a result table
Bright, when foaming foam stabilizer dosage is seldom, foam drilling fluid half-life period of the present invention reaches 7.1d, hence it is evident that is prepared better than conventional blister agent
Foam drilling fluid half-life period, rheological characteristic is good.
The basic performance and rheological property of the foam drilling fluid of table 1
2. heat-resisting property
The embodiment 1-3 prepared foam drilling fluid is taken, loads ageing can, is put into high temp roller furnace, at 120 DEG C
Under, after constant temperature rolls 16h, after taking-up is cooled to room temperature, then high-speed stirred 2min, determine foam drilling fluid basic performance and rheology
Performance.The foaming foam stabilizer (0.2wt%) in embodiment 3 is replaced with into conventional blister agent lauryl sodium sulfate simultaneously
(0.5wt%) is used as reference examples, and other conditions are constant, evaluates its performance to illustrate the effect of the present invention.As a result show, foaming is steady
When infusion dosage is seldom, after 120 DEG C roll aging 16h, half-life period, viscosity somewhat reduce foam drilling fluid of the present invention, and
The half-life period of the more reference examples of foaming agent dosage reduces a lot, and foam drilling fluid temperature resistance of the present invention is up to 120 DEG C.
The heat-resisting property of the foam drilling fluid of table 2
3. anti-salt property
The embodiment 1-3 prepared foam drilling fluid is taken, adds the NaCl of different quality containing, high-speed stirred 2min
Afterwards, foam drilling fluid basic performance and rheological property are determined.The foaming foam stabilizer (0.2wt%) in embodiment 3 is replaced simultaneously
Reference examples are used as conventional blister agent lauryl sodium sulfate (0.5wt%), other conditions are constant, evaluate its performance to illustrate this
The effect of invention.As a result show, foaming foam stabilizer dosage it is seldom when, foam drilling fluid of the present invention with NaCl mass fractions increasing
Add, half-life period and viscosity are slowly increased, and after NaCl mass fractions are more than 4%, half-life period and viscosity slowly decline, and bubble
The half-life period of the more reference examples of agent dosage is reduced quickly, and foam drilling fluid salt resistance of the present invention is polluted up to 10%.
The anti-salt property of the foam drilling fluid of table 3
4. anti-landwaste pollutant performance
The embodiment 1-3 prepared foam drilling fluid is taken, adds the landwaste of different quality containing, high-speed stirred 2min
Afterwards, foam drilling fluid basic performance and rheological property are determined.The foaming foam stabilizer (0.2wt%) in embodiment 3 is replaced simultaneously
Reference examples are used as conventional blister agent lauryl sodium sulfate (0.5wt%), other conditions are constant, evaluate its performance to illustrate this
The effect of invention.As a result show, foaming foam stabilizer dosage it is seldom when, foam drilling fluid of the present invention with landwaste mass fraction increasing
Add, half-life period slowly reduces, and viscosity slowly improves, and the half-life period of the more reference examples of foaming agent dosage reduces quickly, this hair
The bright anti-landwaste of foam drilling fluid is polluted up to 12%.
The anti-landwaste pollutant performance of the foam drilling fluid of table 4
5. rejection
Take a certain amount of drilling cuttings, mesh number is dried between the mesh of 6 mesh~10 at 105 DEG C；It is real that 350ml is added in ageing can
The foam drilling fluid and the dried drilling cuttings of 50.00g of a 1-3 is applied, in 120 DEG C of aging 16h；Solution after aging crosses 40 mesh sieves,
And with running water natural flushing；Drilling cuttings after flushing is dried at 105 DEG C, is weighed, and calculates the mud shale rate of recovery.It will implement simultaneously
Foaming foam stabilizer (0.2wt%) in example 3 replaces with conventional blister agent lauryl sodium sulfate (0.5wt%) and is used as reference examples,
Other conditions are constant, evaluate its performance to illustrate the effect of the present invention.
Dried landwaste is separately taken, landwaste powder is obtained after crushing, prepares evaluation core block (under 4MPa pressure, pressing 5min)；
Dilatometer is opened, evaluation core block is installed, embodiment 1-3 foam drilling fluid is poured into after zeroing；Start to test, record is every
Line swell increment (mm) after 0.5h；Compareed with clear water, calculate line swell increment reduced rate.Simultaneously by the foaming foam stabilizing in embodiment 3
Agent (0.2wt%) replaces with conventional blister agent lauryl sodium sulfate (0.5wt%) and is used as reference examples, and other conditions are constant, comment
Its performance of valency with illustrate the present invention effect.As a result show, when foaming foam stabilizer dosage is seldom, foam drilling fluid mud page of the present invention
The rock rate of recovery and line swell increment reduced rate are higher, and the mud shale rate of recovery and line swell increment of the more reference examples of foaming agent dosage
Reduced rate is relatively low, and foam drilling fluid rejection of the present invention is preferable.
The rejection of the foam drilling fluid of table 5
6. sealing characteristics
The sandstone of 200g different grain sizes (80/120 mesh, 40/80 mesh) is put into middle pressure filter press cup, adds embodiment bubble
Foam drilling fluid, wastage of the measure foam drilling fluid under room temperature 0.7MPa pressure.Simultaneously by the foaming foam stabilizer in embodiment 3
(0.2wt%) replaces with conventional blister agent lauryl sodium sulfate (0.5wt%) and is used as reference examples, and other conditions are constant, evaluation
Its performance with illustrate the present invention effect.As a result show, when foaming foam stabilizer dosage is seldom, foam drilling fluid of the present invention is 80/
Without leakage in 120 mesh sandstones, wastage is relatively low in 40/80 mesh sandstone, and the wastage of the more reference examples of foaming agent dosage
Higher, foam drilling fluid sealing characteristics of the present invention is preferable.
The sealing characteristics of the foam drilling fluid of table 6
Embodiment 4：
The preparation method of foaming foam stabilizer, comprises the following steps described in embodiment 1-3：
(1) 1,3-PD 85ml, epoxychloropropane 200ml, 4-butyl ammonium hydrogen sulfate are added in three-necked flask
Bu4NHSO4(TBAS) 8g, stirred at a temperature of 40 DEG C；The 600ml 50%NaOH aqueous solution is added dropwise with constant pressure funnel, continues
2.5h is stirred at a temperature of 60 DEG C.Upper organic phase is separated with separatory funnel, adds ethanol, heat filtering removes inorganic salts, distillation
Ethanol and epoxychloropropane are removed, obtains ether epoxy, yield 96.7%, purity 90.8%.
(2) 265ml polypropylene tetramers are added in three-necked flask, 65ml is slowly added dropwise dropwise at 0 DEG C with constant pressure funnel
The cold concentrated sulfuric acid, after stirring 2h, mixture is transferred to constant pressure funnel, in three-necked flask plus 200ml 50%NaOH are water-soluble
Liquid, aforementioned mixture is added dropwise at 10 DEG C, stirs 2h.Upper organic phase is separated with separatory funnel, adds ethanol, heat filtering removes nothing
Machine salt, is distilled off ethanol and polypropylene tetramer, obtains different lauryl alcohol, yield 82.6%, purity 92.2%.
(3) the different lauryl alcohol of step (2) product is added in three-necked flask, instills 10ml BF3- diethyl ether solution, stirring a moment
40 DEG C are warming up to, step (1) product ether epoxy is added dropwise under agitation, 80 DEG C are warming up to after dripping off, stirs 5h, is used
The 2%NaOH aqueous solution is neutralized to pH=7, and upper organic phase is separated with separatory funnel, and different lauryl alcohol and ether epoxy is distilled off, obtains
To alcohol ether, yield 81.3%, purity 89.9%.
(4) step (3) product alcohol ether is added in three-necked flask, it is slow dropwise at a temperature of 10 DEG C under stirring
30ml chlorosulfonic acids are added dropwise, HCl gases are removed using device for recovering tail gas, stir 3h, with 2%NaOH ethanol solutions and pH=7,
Ethanol is added, heat filtering removes inorganic salts, ethanol is distilled off, and obtains final product foaming foam stabilizer, yield 90.1%, purity
93.7%.
Infrared spectrum analysis, foaming foam stabilizer manufactured in the present embodiment are shown in Fig. 1 through infrared spectrum analysis.
Results of IR is as shown in figure 1,2854cm-1、2922cm-1For C-H stretching vibration absworption peaks, 1468cm-1
For C-H flexural vibrations absworption peak, 1206cm-1And 1251cm-1For the stretching vibration absworption peak for the C-O being connected with sulfuric ester,
1080cm-1It is corresponding with the functional group for the foam stabilizer molecular structure that bubbles for ehter bond C-O stretching vibration absworption peak, show into
Work(has synthesized designed foaming foam stabilizer.
Mass spectral analysis, foaming foam stabilizer manufactured in the present embodiment are shown in Fig. 2 through mass spectral analysis.
As shown in Fig. 2 the present embodiment bubbles, the molecular weight of foam stabilizer is 764 to mass spectrometry results, sloughs 2 Na+Afterwards
Anion fragment molecular weight is 718, and 2 negative electrical charges of band, mass-to-charge ratio 359 is consistent with mass spectrogram 359.14849 peak,
265.14790 peak is that impurity lauryl sodium sulfate sloughs 1 Na+What anion fragment afterwards was formed, show successfully to synthesize
Designed foaming foam stabilizer.
The reaction equation of the preparation method of described new foaming foam stabilizer is as follows：
Embodiment 5：
The present embodiment is distinguished as with embodiment 4：
The preparation method of the foaming foam stabilizer, comprises the following steps：
(1) 1,3-PD 70ml, epoxychloropropane 150ml, 4-butyl ammonium hydrogen sulfate are added in three-necked flask
Bu4NHSO4(TBAS) 5g, stirred at a temperature of 35 DEG C；The 500ml 50%NaOH aqueous solution is added dropwise with constant pressure funnel, continues
2h is stirred at a temperature of 55 DEG C.Upper organic phase is separated with separatory funnel, adds ethanol, heat filtering removes inorganic salts, and distillation removes
Ethanol and epoxychloropropane are removed, obtains ether epoxy, yield 93.0%, purity 90.1%.
(2) 200ml polypropylene tetramers are added in three-necked flask, are slowly dripped dropwise at a temperature of 0 DEG C with constant pressure funnel
Add the cold concentrated sulfuric acids of 60ml, after stirring 2h, mixture is transferred to constant pressure funnel, 150ml 50% is added in three-necked flask
The NaOH aqueous solution, aforementioned mixture is added dropwise at a temperature of 10 DEG C, stirs 2h.Upper organic phase is separated with separatory funnel, adds second
Alcohol, heat filtering remove inorganic salts, ethanol and polypropylene tetramer are distilled off, obtains different lauryl alcohol, yield 80.8%, purity
91.0%.
(3) the different lauryl alcohol of step (2) product is added in three-necked flask, instills 5ml BF3- diethyl ether solution, stirring a moment
35 DEG C are warming up to, step (1) product ether epoxy is added dropwise under agitation, 75 DEG C are warming up to after dripping off, stirs 4h, is used
The 2%NaOH aqueous solution is neutralized to pH=7, and upper organic phase is separated with separatory funnel, and different lauryl alcohol and ether epoxy is distilled off, obtains
To alcohol ether, yield 80.4%, purity 88.1%.
(4) step (3) product alcohol ether is added in three-necked flask, under agitation, is slowly dripped dropwise at a temperature of 5 DEG C
Add 30ml chlorosulfonic acids, HCl gases are removed using device for recovering tail gas, stir 3h, with 2%NaOH ethanol solutions and pH=7, are added
Enter ethanol, heat filtering removes inorganic salts, ethanol is distilled off, and obtains final product foaming foam stabilizer, yield 88.9%, purity
90.5%.
Embodiment 6：
The present embodiment is distinguished as with embodiment 5：
The preparation method of the foaming foam stabilizer, comprises the following steps：
(1) 1,3-PD 100ml, epoxychloropropane 250ml, 4-butyl ammonium hydrogen sulfate are added in three-necked flask
Bu4NHSO4(TBAS) 15g, stirred at a temperature of 45 DEG C；The 650ml 50%NaOH aqueous solution is added dropwise with constant pressure funnel, continues
3h is stirred at a temperature of 65 DEG C.Upper organic phase is separated with separatory funnel, adds ethanol, heat filtering removes inorganic salts, and distillation removes
Ethanol and epoxychloropropane are removed, obtains ether epoxy, yield 95.5%, purity 94.2%.
(2) 300ml polypropylene tetramers are added in three-necked flask, 70ml is slowly added dropwise dropwise at 0 DEG C with constant pressure funnel
The cold concentrated sulfuric acid, after stirring 3h, mixture is transferred to constant pressure funnel, in three-necked flask plus 250ml 50%NaOH are water-soluble
Liquid, aforementioned mixture is added dropwise at 20 DEG C, stirs 3h.Upper organic phase is separated with separatory funnel, adds ethanol, heat filtering removes nothing
Machine salt, is distilled off ethanol and polypropylene tetramer, obtains different lauryl alcohol, yield 83.6%, purity 90.8%.
(3) the different lauryl alcohol of step (2) product is added in three-necked flask, instills 10ml BF3- diethyl ether solution, stirring a moment
45 DEG C are warming up to, step (1) product ether epoxy is added dropwise under agitation, 85 DEG C are warming up to after dripping off, stirs 6h, is used
The 2%NaOH aqueous solution is neutralized to pH=7, and upper organic phase is separated with separatory funnel, and different lauryl alcohol and ether epoxy is distilled off, obtains
To alcohol ether, yield 82.4%, purity 90.2%.
(4) step (3) product alcohol ether is added in three-necked flask, it is under agitation, slow dropwise at a temperature of 15 DEG C
40ml chlorosulfonic acids are added dropwise, HCl gases are removed using device for recovering tail gas, stir 4h, with 2%NaOH ethanol solutions and pH=7,
Ethanol is added, heat filtering removes inorganic salts, ethanol is distilled off, and obtains final product foaming foam stabilizer, yield 89.3%, purity
92.8%.
Test example 2：Foaming foam stabilizer performance evaluation prepared by embodiment 4
1. surface tension
The surface tension of the foaming foam stabilizer aqueous solution of various concentrations is tested, as a result as shown in figure 3, with foaming foam stabilizing
The increase surface tension of agent concentration gradually reduces, and when concentration increases to 0.2%, surface tension is down to 20.40mNm-1, it is purer
Water surface tension reduces 71.82%, shows the foaming foam stabilizer of the embodiment of the present invention 4 and has stronger surface-active, is advantageous to
Improve frothing capacity.
2. frothing capacity is tested
Frothing capacity is primarily referred to as foamability and foam stability.Foam volume V0Reflect foamability, analysis liquid half
Decline phase t1/2Reflect foam stability.Frothing capacity tests the foam volume of the new foaming foam stabilizer of various concentrations
And half-life period, as a result as shown in Figure 4, it is known that foaming foam stabilizer mass fraction foam volume at 0.2% reaches 610ml, partly declines
Phase reaches 1440s, continues to improve mass fraction, and frothing capacity is increased slightly but unobvious, shows what the embodiment of the present invention 4 was developed
Foaming foam stabilizer has preferable foaming effect in low concentration, and foam number is big, and foam stability is good.
The foaming foam stabilizer of test quality fraction 0.2%, 0.5% conventional foaming agent and Gemini surface active respectively
Foam volume and half-life period of the agent under identical foaming condition, to evaluate its frothing capacity.Method of testing reference《SY/T 5350-
2009 drilling fluids foaming agent assessment process》, test result is shown in Table 1, and contrast is understood, the surface described in the embodiment of the present invention 4 is lived
The property new foaming foam stabilizer of agent class can reach higher foaming effect in low concentration, foam volume and half-life period compared with
Height, half-life period improve more than 3 times.
The different foaming agent frothing capacity tests of table 8
3. anti-salt property
The anti-salt property of foaming foam stabilizer is primarily referred to as the ability of anti-NaCl pollutions.It is steady in the foaming of mass fraction 0.2%
In infusion solution, the NaCl of different quality containing is added, evaluates its anti-salt property, as a result as shown in figure 5, NaCl dosages are 3%
Within when, the foam volume of new foaming foam stabilizer and half-life period slightly reduce, and the range of decrease shows the embodiment of the present invention than shallower
The 4 foaming foam stabilizers developed have preferable anti-salt property.
Claims (10)
1. a kind of novel foam drilling fluid system, it is characterised by being made up of following component：
0.2wt% foaming foam stabilizers；
0.2wt% foam stabilizers；
0.8wt% tackifier；
0.2wt% fluid loss additives；
0.1wt%~1wt% weighting agents；
Surplus is water；Wherein the benchmark of the mass percent of each component is water.
2. novel foam drilling fluid system according to claim 1, it is characterised in that：The molecular formula of the foaming foam stabilizer
As shown in formula (I)：
3. novel foam drilling fluid system according to claim 1, it is characterised in that：The foam stabilizer is carboxymethyl cellulose
Element, outward appearance：White, it is odorless, tasteless, have hygroscopicity particle；Moisture≤7%；PH=7.0~8.0；(sieve aperture 0.9mm is sieved fineness
It is remaining)≤8%.
4. novel foam drilling fluid system according to claim 1, it is characterised in that：The foam stabilizer is biopolymer
XC, outward appearance：Pale yellow powder；Moisture≤8%；PH=7.0~8.0；Fineness (sieve aperture 0.9mm is tailed over)≤5%.
5. novel foam drilling fluid system according to claim 1, it is characterised in that：The tackifier are polyanion fibres
Tie up chlorins compound, outward appearance：White powder；Moisture≤6%；PH=7.0~8.0；Inherent viscosity 100ml/g：≥9；Fineness (sieve
Hole 0.9mm is tailed over)≤6%.
6. novel foam drilling fluid system according to claim 1, it is characterised in that：The tackifier are hydroxy ethyl fibers
Element, outward appearance：White powder；Moisture≤6%；PH=7.0~8.0；Inherent viscosity 100ml/g：≥8；(sieve aperture 0.9mm is sieved fineness
It is remaining)≤8%.
7. novel foam drilling fluid system according to claim 1, it is characterised in that：The fluid loss additive is walchowite
Or hydroxypropul starch；Walchowite, outward appearance：Dark brown powder；Moisture≤10%；Water-insoluble≤10%；HTHP leak-off
Amount≤20ml；Hydroxypropul starch, outward appearance：White powder；Moisture≤11%；Water-insoluble≤9%；High temperature and high pre ssure filtration≤
18ml。
8. novel foam drilling fluid system according to claim 2, it is characterised in that：The preparation side of the foaming foam stabilizer
Method, different lauryl alcohol is in catalyst BF3The effect of-diethyl ether solution is lower to generate alcohol ether with ether epoxy reaction, then successively with chlorosulfonic acid, hydrogen
Sodium oxide molybdena reaction generates the foaming foam stabilizer.
9. novel foam drilling fluid system according to claim 8, it is characterised in that：The preparation side of the foaming foam stabilizer
Method, including following steps：
(1) 1,3- propane diols, epoxychloropropane and 4-butyl ammonium hydrogen sulfate are mixed；The 50%NaOH aqueous solution is instilled, after
Continuous stirring；Organic phase is separated after liquid separation, ethanol is added in organic phase, heat filtering removes inorganic salts, ethanol and ring is distilled off
Oxygen chloropropane, obtains ether epoxy；
(2) cold concentrated sulfuric acid stirring is slowly added dropwise in polypropylene tetramer, obtained mixture is added dropwise in the 50%NaOH aqueous solution,
Stirring, organic phase is separated after liquid separation, and ethanol is added in organic phase, and heat filtering removes inorganic salts, and ethanol and four is distilled off and gathers
Propylene, obtain different lauryl alcohol；
(3) BF is instilled in different lauryl alcohol prepared by step (2)3- diethyl ether solution, stirring, heating, is added dropwise step (1) under agitation
The ether epoxy of preparation, heating stirring, is neutralized to pH=7 with the 2%NaOH aqueous solution, separates organic phase after liquid separation, be distilled off different
Lauryl alcohol and ether epoxy, obtain alcohol ether；
(4) in alcohol ether prepared by step (3), agitation and dropping chlorosulfonic acid removes HCl gases, and stirring is molten with 2%NaOH ethanol
Liquid is neutralized to pH=7, adds ethanol, and heat filtering removes inorganic salts, ethanol is distilled off, obtains the foaming foam stabilizer.
10. the preparation method of novel foam drilling fluid system according to any one of claim 1 to 9, including following step
Suddenly：
(1) add water in jar, turn on agitator is stirred under the conditions of 10000r/min~12000r/min；
(2) foam stabilizer is added, continuing stirring makes it fully dissolve, and then adds the tackifier, and continuing stirring fills it
Divide dissolving, add the fluid loss additive, continuing stirring makes it fully dissolve, and adds the weighting agent, and continuing stirring makes it
It is fully dispersed to be uniformly eventually adding the foaming foam stabilizer, continue stirring 1min~3min and be prepared into the foam drilling liquid
System.
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| CN107523278A (en) * | 2017-07-06 | 2017-12-29 | 中联煤层气有限责任公司 | A kind of new foaming foam stabilizer and preparation method thereof |
| CN112457828A (en) * | 2020-12-02 | 2021-03-09 | 中联煤层气有限责任公司 | Use and maintenance method of micro-foam drilling fluid |
| CN113122200A (en) * | 2019-12-31 | 2021-07-16 | 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 |
| CN113122201A (en) * | 2019-12-31 | 2021-07-16 | 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 |
| CN113969147A (en) * | 2020-07-23 | 2022-01-25 | 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 |
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| CN107523278A (en) * | 2017-07-06 | 2017-12-29 | 中联煤层气有限责任公司 | A kind of new foaming foam stabilizer and preparation method thereof |
| CN107523278B (en) * | 2017-07-06 | 2020-06-02 | 中联煤层气有限责任公司 | Novel foaming foam stabilizer and preparation method thereof |
| CN113122200A (en) * | 2019-12-31 | 2021-07-16 | 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 |
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| 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 |
| CN113969147A (en) * | 2020-07-23 | 2022-01-25 | 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 |
| 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 |
| CN112457828A (en) * | 2020-12-02 | 2021-03-09 | 中联煤层气有限责任公司 | Use and maintenance method of micro-foam drilling fluid |
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| CN107502321B (en) | 2020-06-02 |
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