CN107505432A - A kind of evaluation method for quantitative determining shale intercalator and suppressing clay surface hydration ability - Google Patents
A kind of evaluation method for quantitative determining shale intercalator and suppressing clay surface hydration ability Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
- G01N5/045—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder for determining moisture content
Abstract
The invention belongs to oil gas field drilling technique field, is used in particular to one kind in oilfield drilling operation, bores and meets in the stratum rich in clay mineral, and quantitative determination shale intercalator suppresses the evaluation method of clay surface hydration ability.The invention mainly includes steps：Prepare intercalation organoclay；Intercalation clay isothermal adsorption；Pass through X ray diffraction method measurement bases bottom spacing；Intercalation clay adsorption water type and content are calculated by thermogravimetic analysis (TGA) method；Determine the cation exchange capacity of intercalation clay.Beneficial effects of the present invention：Method And Principle is reliable, easy to operate, can quantitative assessment clay surface hydration degree, and the rejection of quantitative assessment intercalation inhibitor, the evaluation method that shale intercalator suppresses clay surface hydration degree is established, the Wellbore Stability of sludge shale formation is solved, has broad application prospects.
Description
Technical field
The present invention relates to one kind to be used in oilfield drilling operation, bores and meets in the stratum rich in clay mineral, quantitative determination
Shale intercalator suppresses the evaluation method of clay surface hydration ability.
Background technology
Shale gas is a kind of important unconventional gas resource commercialized in the world.China's shale gas is opened
Hair is still in the starting stage, mainly carries out development experiments in the Sichuan Basin and its periphery at present.The reservoir in the Sichuan Basin is hard crisp
Property shale, stratification, microfissure relatively develop, and easy aquation disperses, easily degraded in shale gas drilling process, chip off-falling etc. seriously
Borehole well instability problem.Hole instability frequently results in the problems such as cave-in, undergauge, bit freezing, adds drilling time and brill
Well cost.75% hole instability occurs mainly in mud shale stratum, particularly water-sensitive strata.For shale gas into Tibetan
Feature, horizontal well have turned into the main drilling mode of shale gas exploitation.Compared with conventional horizontal well, shale horizontal well horizontal segment compared with
It is long, 1000~2000m is typically in the range of, the time that drilling fluid contacts with stratum increases, and Shale Hydration is more serious.
60~70% shale gas horizontal wells of foreign countries use oil base drilling fluid system, the shale gas horizontal well that the country completes at present
The overwhelming majority uses oil base drilling fluid system, and oil base drilling fluid has the advantages of borehole wall stability is good, rejection ability is strong, but exists
Not environmentally, the shortcomings of cost is of a relatively high.Water-base drilling fluid can overcome the shortcomings that oil base drilling fluid just, but at this stage water base
Suppression of the drilling fluid to mud stone or strong retraction shale formation still has problem, it is necessary to targetedly further investigate.Mud page
The essence of rock aquation is the hydration swelling of clay mineral in mud shale.It is swollen that commercialization inhibitor at this stage can suppress infiltration aquation
It is swollen, extend the hydration time, but without the inhibitor for suppressing surface hydration.
At this stage also there is different degrees of limitation in the research meanses to wellbore stability and experimental method, and it is deep to lack system
The Quantitative study entered, it is difficult to determine reasonable benefit/risk Density Window under drilling fluid hydration, it is impossible to meet that anti-sloughing technique quantifies
The needs of optimizing research.The strong and weak evaluation of hydration, relies primarily on rolling after being contacted at this stage to mud shale with drilling fluid
The rate of recovery, shale linear expansion rate, CST values and Classification of Shales method evaluate shale hydration, but these methods are big
It is qualitative or sxemiquantitative mostly, can also obtains opposite conclusion sometimes.Document《The heat analysis quantitative study side of clay bound water
Method》Isothermal adsorption clay bound water is measured by heat analysis, but combination water of the clay in liquid aqueous systems can not be measured and contained
Amount.Patent publication No. 104297096A《A kind of method for quantitative determining clay bound water content》Describe determining for clay bound water
Amount analysis, can carry out the evaluation of relativity, but can not quantitative determine clay surface hydration, can not evaluation of measuring intercalator
Rejection.In summary, the evaluation side of clay surface hydration is also suppressed outside Current Domestic without energy quantitative measurment intercalator
Method, it is therefore necessary to establish the evaluation method that quantitative assessment intercalator suppresses clay surface hydration, suppress surface hydration for research
Provide fundamental basis, reference is provided to develop the efficient shale control agent of suppression clay surface hydration；Help to establish and bore shale
Long well section water base drilling fluid for horizontal wells, solve shale long well section wellbore stability, contribute to water-base drilling fluid to substitute oil base and bore
Well liquid.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of shale intercalator that quantitative determines to suppress clay surface hydration ability
Evaluation method, this method principle is reliable, easy to operate, can quantitative assessment clay surface hydration degree, and quantitative assessment intercalation press down
The rejection of preparation, the evaluation method that shale intercalator suppresses clay surface hydration degree is established, with solving sludge shale
The Wellbore Stability of layer, has broad application prospects.
Technical scheme is as follows：
A kind of evaluation method for quantitative determining shale intercalator and suppressing clay surface hydration ability, this method include following step
Suddenly：
S1：Clay prepares intercalation organoclay with intercalator by stirring, centrifugation, precipitation, drying；
S2：Intercalation clay isothermal adsorption；
S3：The substrate spacing of intercalation clay is measured by X-ray diffraction method；
S4：Intercalation clay adsorption water type and content are calculated by thermogravimetic analysis (TGA) method；
S5：Determine the cation exchange capacity of intercalation clay；
S6：Quantitative intercalation clay adsorption water type and content, the degree of hydration of quantitative assessment intercalation clay, accurate measurement are inserted
Cation exchange capacity, the rejection of quantitative assessment intercalator of layer clay.
Clay is dried to constant weight under the conditions of 150 DEG C in the S1, prepares 1~3% intercalant solution, will be a certain amount of
Drying clay add intercalant solution in stir 24h, suspension is taken out, import centrifuge tube in, be filtrated to get sediment；
Remaining suspension pours out upper liquid, adds deionized water, is well mixed, 10min is centrifuged under 4000rpm rotating speed, falls
Go out supernatant, repeat and obtain sediment three times, the sediment obtained twice is dried in vacuo at 80 DEG C, grinding, crosses 200 mesh
Sieve (74 μm), constant weight is dried under the conditions of 150 DEG C.
A certain amount of deionized water (electrical conductivity is 18.25M Ω .cm) is added in the dry device of cleaning in the S2, according to
Bibliography checks in the solubility and activity of different inorganic salts at different temperatures, inorganic salts is sequentially added into, at 20~30 DEG C
Isothermal equilibrium one day, 1g or so na montmorillonite is separately added into measuring cup, weighs its quality and record, measuring cup is distinguished
In drier corresponding to being put into, drier lid is covered, isothermal adsorption equilibrium, is taken out with clean paper tape, on electronic balance
Weigh its quality and record, according to《Several organic slat solution activity and inhibition experimental study》, it is calculated by formula (1) flat
Weigh water absorption, and formula (1) is as follows：
In formula：m0For the quality of measuring cup, g；m1For the quality of measuring cup and clay, g；m2After isothermal adsorption equilibrium, claim
The quality of measuring bottle and clay, g；m3After isothermal adsorption equilibrium, the quality of measuring cup, g.
The intercalation clay of different activity isothermal adsorption equilibriums is taken out in told S3, is sealed, opens computer, water cooling system
System etc., regulation hydraulic pressure flow is more than 3.8L/min；Start main frame, open process of measurement, according to first up voltage (40KV), rise electricity again
The order of (40mA) is flowed, sets the voltage and current of work；Set angle of diffraction scope：3 °~40 °, start application program, root
According to bragg's formula：2dsin θ=n λ, the substrate spacing of intercalation clay is calculated, n is diffraction progression in formula, here n=1；θ is to spread out
Penetrate half-angle；λ is the wavelength of target, here。
Experiment condition is set in the S4：30~300 DEG C of temperature range；10~30 DEG C/min of heating rate；Protect gas
20mL/min；Purge gas 60mL/min, pass through DTG curves (first-order derivative of the TG curves to temperature) and D2(TG is bent for TG curves
Line is to the second derivative of temperature, first-order derivative of the DTG curves to temperature) step on TG curves is determined, quantitatively distinguish intercalation and stick
Soil absorption water type and content.The absorption water content of the different steps calculated by formula (2), formula are as follows：
In formula：W is the percentage that the 1st step or the 2nd step adsorpting water quantity account for dry ground quality；m1,2For the 1st step or
2nd step adsorpting water quantity, g；M be dry ground and adsorb water gross mass, g.
According to the measure of professional standard LY/T-1243-1999 forest soil cation exchange capacity (CEC)s in the S5, intercalation is determined
Clay, the cation exchange capacity CEC values calculated by formula (3), formula are as follows：
In formula：CEC is cation exchange capacity, mmol/100g；C be hydrochloric acid standard solution concentration, mol/L；V is salt
The dosage of sour standard liquid, mL；V0For the dosage of blank test hydrochloric acid standard solution, mL；m1For drying sample quality, g.
Pass through the quantitative intercalation clay adsorption water type of experimental data and content, the water of quantitative assessment intercalation clay in the S6
Change degree, the cation exchange capacity of accurate measurement intercalation clay, the rejection of quantitative assessment intercalator.
Beneficial effects of the present invention are：
(1) intercalation clay adsorption water type and content, quantitative assessment intercalation clay can be quantified by this experimental method
Degree of hydration, the cation exchange capacity of accurate measurement intercalation clay, the rejection of quantitative assessment intercalator；
(2) existing method is come to evaluate shale hydration be qualitative or sxemiquantitative mostly at present, and existing method is
Relatively independent research, it is impossible to carry out comprehensive evaluation, theoretical foundation of this experimental method based on science, largely derive,
Calculate, experimental result comprehensive can be evaluated intercalator, more complete relative to art methods, this experimental method
Face, it is comprehensive stronger, experimental period can be saved, efficiently.
Brief description of the drawings
, below will be to required use in embodiment in order to illustrate more clearly of the technical scheme of embodiment of the present invention
Accompanying drawing be briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not to be seen as
It is the restriction to scope, for those of ordinary skill in the art, on the premise of not paying creative work, can be with root
Other related accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the inventive method block diagram；
Fig. 2 is unit absorption of the na montmorillonite under different relative humidity after hexamethylene diamine of the present invention and polyethyleneimine intercalation
Water；
Fig. 3 is the interlamellar spacing of na montmorillonite isothermal adsorption after hexamethylene diamine of the present invention and polyethyleneimine intercalation；
Fig. 4 is the DTG curves of na montmorillonite after hexamethylene diamine intercalation of the present invention；
Fig. 5 is the DTG curves of na montmorillonite after polyethyleneimine intercalation of the present invention.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
As shown in figure 1, the present invention is a kind of evaluation side for quantitative determining shale intercalator and suppressing clay surface hydration ability
Method, this method mainly include the following steps that：Prepare intercalation organoclay；Intercalation clay isothermal adsorption；Surveyed by X-ray diffraction method
Measure the substrate spacing of intercalation clay；Intercalation clay adsorption water type and content are calculated by thermogravimetic analysis (TGA) method；Measure intercalation sticks
The cation exchange capacity of soil.
Na montmorillonite is dried to constant weight under the conditions of 150 DEG C in the S1, prepares 1~3% intercalant solution, intercalation
Agent includes hexamethylene diamine, polyethyleneimine, and the na montmorillonite of a certain amount of drying is added in intercalant solution and stirs 24h, will be outstanding
Supernatant liquid takes out, and imports in centrifuge tube, is filtrated to get sediment；Remaining suspension pours out upper liquid, adds deionized water, mixes
Close uniformly, centrifuge 10min under 4000rpm rotating speed, pour out supernatant, repeat and obtain sediment three times, will obtain twice
The sediment arrived is dried in vacuo at 80 DEG C, grinding, crosses 200 mesh sieve (74 μm), constant weight is dried under the conditions of 150 DEG C.Wherein
Clay raw material carrys out the na montmorillonite of free NANOCOR companies, and hexamethylene diamine and polyethyleneimine are both from commercially available.
In the S2 a certain amount of deionized water (electrical conductivity is 18.25M Ω .cm) is added in the dry device of cleaning), according to
Bibliography checks in the solubility and activity of different inorganic salts at different temperatures, inorganic salts is sequentially added into, at 20~30 DEG C
Isothermal equilibrium one day, 1g or so na montmorillonite is separately added into measuring cup, weighs its quality and record, measuring cup is distinguished
In drier corresponding to being put into, drier lid is covered, isothermal adsorption equilibrium, is taken out with clean paper tape, on electronic balance
Weigh its quality and record, according to《Several organic slat solution activity and inhibition experimental study》, it is calculated by formula (1) flat
Weigh water absorption, and formula (1) is as follows：
In formula：m0For the quality of measuring cup, g；m1For the quality of measuring cup and na montmorillonite, g；m2For isothermal adsorption equilibrium
Afterwards, the quality of measuring cup and na montmorillonite, g；m3After isothermal adsorption equilibrium, the quality of measuring cup, g.
Adsorption isotherm experiment relative error ± 5%, variance are less than a ten thousandth, and standard deviation is less than 2/1000ths, experiment knot
Fruit sees Fig. 2.From figure 2 it can be seen that the na montmorillonite isothermal adsorption water after hexamethylene diamine and polyethyleneimine intercalation is respectively less than
The isothermal adsorption water of na montmorillonite, the isothermal adsorption water of polyethyleneimine-montmorillonite system are more than hexamethylene diamine-montmorillonite body
The isothermal adsorption water of system.For hexamethylene diamine-na montmorillonite system when relative humidity is less than 0.9, its clay unit adsorpting water quantity is small
Unit adsorpting water quantity when pure na montmorillonite is in relative humidity 0.25, when being less than 0.25 due to relative humidity, hydrone is main
Absorption forms one layer of aquation in na montmorillonite outer surface and in interlayer, illustrate after hexamethylene diamine intercalated montmorillonite possibility between cheating engaging layer
Also one layer of hydrone.Polyethyleneimine-na montmorillonite system is when relative humidity is less than 0.9, its clay unit adsorpting water quantity
More than unit adsorpting water quantity of the pure na montmorillonite in relative humidity 0.25, its possible cause is that hexamethylene diamine insertion na montmorillonite is brilliant
The arrangement mode of layer is dense individual layer tiling, although the arrangement mode and single flat of polyethyleneimine insertion na montmorillonite
Paving, but be not dense individual layer tiling, therefore there are more holes between polyethyleneimine-sodium montmorillonite crystal layer, it can adsorb
More hydrone.But when polyethyleneimine-na montmorillonite system unit adsorpting water quantity is less than na montmorillonite relative humidity 0.5
Unit adsorpting water quantity, so also it shows that montmorillonite crystal layer also only exists one layer of hydrone of receiving after polyethyleneimine intercalated montmorillonite
Possibility.This explanation hexamethylene diamine and polyethyleneimine can suppress water and adsorb the ability on na montmorillonite.
The intercalated montmorillonite of different activity isothermal adsorption equilibriums is taken out in told S3, is sealed, opens computer, water cooling
System etc., regulation hydraulic pressure flow is more than 3.8L/min；Start main frame, open process of measurement, according to first up voltage (40KV), rise again
The order of electric current (40mA), set the voltage and current of work；Set angle of diffraction scope：3 °~40 °, start application program,
According to bragg's formula：2dsin θ=n λ, the substrate spacing of intercalation clay is calculated, n is diffraction progression in formula, here n=1；θ is
Diffraction half-angle；λ is the wavelength of target, here
As shown in figure 3, the na montmorillonite before and after isothermal adsorption by hexamethylene diamine and polyethyleneimine intercalation na montmorillonite
Crystal layer spacing has almost no change.The crystal layer spacing of na montmorillonite is after 1.32nm, polyethyleneimine intercalation after hexamethylene diamine intercalation
The crystal layer spacing of na montmorillonite in 1.39nm, its interlamellar spacing less times greater than the interlamellar spacing of hexamethylene diamine be due to branched polyethylene imine
Space structure caused by.Because the interlamellar spacing that montmorillonite crystal layer adsorbs 1 layer of hydrone is~1.25nm or so, montmorillonite crystal layer
The crystal layer spacing of 2 layers of hydrone of absorption is~1.5nm or so.And after hexamethylene diamine and polyethyleneimine intercalation na montmorillonite crystal layer
Spacing is more than 1.25nm, less than 1.5nm.Na montmorillonite interlayer has 1 layer of water of receiving after illustrating hexamethylene diamine and polyethyleneimine intercalation
The space of molecule, but without the space for accommodating two layers of hydrone.
Experiment condition is set in the S4：30~300 DEG C of temperature range；10~30 DEG C/min of heating rate；Protect gas
20mL/min；Purge gas 60mL/min, pass through DTG curves (first-order derivative of the TG curves to temperature) and D2(TG is bent for TG curves
Line is to the second derivative of temperature, first-order derivative of the DTG curves to temperature) step on TG curves is determined, quantitatively distinguish intercalation and stick
Soil absorption water type and content.
As shown in figure 4, occurring two peaks after hexamethylene diamine intercalation on the DTG curves of clay, illustrate occur on TG curves
Two steps.One peak valley of DTG curves appears in 150 DEG C of effects, and corresponding is particle exterior surface absorption water；Another peak valley
230 DEG C or so are appeared in, corresponding is clay crystalline substance interlayer surface water.As shown in figure 5, na montmorillonite after polyethyleneimine intercalation
There was only a low temperature peak valley on DTG curves, be the absorption water of particle exterior surface corresponding to low temperature peak valley.Peak valley temperature is at 160 DEG C
Left and right, with the increase of relative humidity, low temperature peak valley moves to low temperature direction, and peak shape narrows from the width, from light to dark.Temperature is more than
At 280 DEG C, the DTG curves of low relative humidity have a downtrend, are the decomposition of branched polyethylene imine corresponding to this.By
In there is no high temperature peak valley, therefore there is no interlayer hydrone, illustrate that branched polyethylene imine can completely inhibit surface hydration.Pass through formula
(2) the absorption water content of the different steps calculated, formula are as follows：
In formula：W is the percentage that the 1st step or the 2nd step adsorpting water quantity account for dry ground quality；m1,2For the 1st step or
2nd step adsorpting water quantity, g；M be dry ground and adsorb water gross mass, g.m1,2To pass through DTG curves and D2TG curves determine TG
Step on curve obtains the 1st step or the 2nd step adsorpting water quantity, if only the 2nd step does not have first step, m1=0.
M is the initial mass i.e. dry ground quality and the summation for adsorbing water quality, m-m of TG curves1-m2Obtain dry ground quality.1st step or
The absorption water quality divided by dry ground quality of the step of person the 2nd are equal to the ratio of every gram of dry ground absorption different type absorption water.
By above-mentioned calculating, table 1 is obtained, as known from Table 1, hexamethylene diamine-montmorillonite system has two steps on TG curves,
Illustrate that isothermal adsorption water has two types, the absorption water of particle exterior surface corresponding to the 2nd step, be corresponding to the 1st step cover it is de-
Absorption water in native crystal layer.The water content of 2nd step increases with the increase of relative humidity, and the water content of the 1st step is with phase
It is the oriented particle exterior surface absorption water of adsorbed water to have the reason for trend slightly reduced, reduction to the increase of humidity
The trend of migration, this part adsorbed water of migration is actually interlayer surface absorption water.The appearance of 1st step illustrates layer
Between adsorb the presence of water, it was demonstrated that hexamethylene diamine can not completely inhibit surface hydration, between the substrate with reference to hexamethylene diamine+montmorillonite system
Away from 1.32nm, illustrate one layer of hydrone in hexamethylene diamine+montmorillonite system be present.Polyethyleneimine+montmorillonite system is bent in TG
Line only has a step, i.e. the 2nd step.The temperature range of this step is similar to the 2nd step of hexamethylene diamine+montmorillonite system,
Illustrate particle appearance absorption water in polyethyleneimine+montmorillonite system isothermal adsorption be present.But polyethyleneimine+montmorillonite body
System illustrates adsorbed water is not present without there is the 1st step, it was demonstrated that BPEI can completely inhibit surface hydration.
Table 1：The heat analysis data of intercalated montmorillonite isothermal adsorption
According to the measure of professional standard LY/T-1243-1999 forest soil cation exchange capacity (CEC)s in the S5, intercalation is determined
Clay, the cation exchange capacity CEC values calculated by formula (3), formula are as follows：
In formula：CEC is cation exchange capacity, mmol/100g；C be hydrochloric acid standard solution concentration, mol/L；V is salt
The dosage of sour standard liquid, mL；V0For the dosage of blank test hydrochloric acid standard solution, mL；m1For drying sample quality, g.
By above-mentioned calculating, table 2 is obtained, as known from Table 2, hexamethylene diamine and polyethyleneimine can orient insertion as intercalator
Clay, compensating cation is replaced, reduce the CEC values of intercalation clay.But polyethyleneimine can more reduce sodium than hexamethylene diamine and cover and take off
The CEC values of soil, illustrate that polyethyleneimine can replace more compensating cations between sodium montmorillonite crystal layer than hexamethylene diamine, divide with reference to hot
Analyse experimental result, it was demonstrated that polyethyleneimine can completely inhibit surface hydration, and hexamethylene diamine can not completely inhibit surface hydration.
The cation exchange capacity CEC values of the intercalated montmorillonite of table 2
The adsorption isotherm experiment of intercalation organoclay at different temperatures is carried out by preparing intercalation organoclay, measuring intercalation has
Machine soil isothermal adsorption water is much smaller than the isothermal adsorption water of pure clay, illustrates that intercalator has the ability for suppressing water absorption.It is logical
Cross substrate spacing of the X-ray diffraction method measurement measurement intercalation organoclay before and after isothermal adsorption.After experiment measures hexamethylene diamine intercalation
The crystal layer spacing of the crystal layer spacing of na montmorillonite na montmorillonite after 1.32nm, polyethyleneimine intercalation is in 1.39nm.Due to covering
The interlamellar spacing that de- native crystal layer adsorbs 1 layer of hydrone is~1.25nm or so, montmorillonite crystal layer adsorbs the crystal layer spacing of 2 layers of hydrone
Be~1.5nm or so.And the crystal layer spacing of na montmorillonite is more than 1.25nm after hexamethylene diamine and polyethyleneimine intercalation, it is less than
1.5nm.Na montmorillonite interlayer has the space for accommodating 1 layer of hydrone after illustrating hexamethylene diamine and polyethyleneimine intercalation, but does not hold
Receive the space of two layers of hydrone.Intercalation na montmorillonite is calculated by thermogravimetic analysis (TGA) method and adsorbs water type and content, hexamethylene diamine-illiteracy
The de- soil body, which is tied up on TG curves, two steps, illustrates that isothermal adsorption water has two types, particle exterior surface corresponding to the 2nd step
Absorption water, be absorption water in montmorillonite crystal layer corresponding to the 1st step.The appearance of 1st step illustrates depositing for adsorbed water
, it was demonstrated that hexamethylene diamine can not completely inhibit surface hydration, with reference to the substrate spacing 1.32nm of hexamethylene diamine+montmorillonite system, say
Understand in hexamethylene diamine+montmorillonite system one layer of hydrone be present.Polyethyleneimine+montmorillonite system only has a platform in TG curves
Rank, i.e. the 2nd step.The temperature range of this step is similar to the 2nd step of hexamethylene diamine+montmorillonite system, illustrates polyethyleneimine
Particle appearance absorption water in amine+montmorillonite system isothermal adsorption be present.But polyethyleneimine+montmorillonite system does not occur the
1 step, illustrate adsorbed water is not present, it was demonstrated that BPEI can completely inhibit surface hydration.By the sun for determining intercalation clay
Ion exchange capacity finds that hexamethylene diamine and polyethyleneimine can orient insertion na montmorillonite as intercalator, displacement compensation it is positive from
Son, reduce the CEC values of intercalation na montmorillonite.But polyethyleneimine can more reduce the CEC values of na montmorillonite, explanation than hexamethylene diamine
Polyethyleneimine can replace more compensating cations between sodium montmorillonite crystal layer than hexamethylene diamine, with reference to thermal analysis experiment result, card
Clear polyethyleneimine can completely inhibit surface hydration, and hexamethylene diamine can not completely inhibit surface hydration, therefore the suppression of intercalator
Performance is polyethyleneimine ＞ hexamethylene diamines.In summary, by preparing intercalation organoclay, intercalation clay isothermal adsorption, X- is passed through
Ray diffraction method measurement base bottom spacing, intercalation clay adsorption water type and content are calculated by thermogravimetic analysis (TGA) method and measure is inserted
The cation exchange capacity serial of methods of layer clay can quantify intercalation clay adsorption water type and content, quantitative assessment intercalation
The degree of hydration of clay, the cation exchange capacity of accurate measurement intercalation clay, the rejection of quantitative assessment intercalator.Existing rank
Also there is different degrees of limitation in section, the deep quantification of shortage system is ground to the research meanses and experimental method of wellbore stability
Study carefully, it is difficult to determine reasonable benefit/risk Density Window under drilling fluid hydration, it is impossible to meet the need of anti-sloughing technique quantitative optimization research
Will.The strong and weak evaluation of hydration after being contacted at this stage to mud shale with drilling fluid, relies primarily on rolling rate of recovery, shale line
Property expansion rate, CST values and Classification of Shales method evaluate shale hydration, but these methods are qualitative mostly or half
Quantitative, opposite conclusion can be also obtained sometimes, and existing method is relatively independent research, it is impossible to carry out comprehensive comment
Valency, theoretical foundation of this experimental method based on science, largely derive, calculate, experimental result can be comprehensive to intercalation
Agent is evaluated, and relative to art methods, this experimental method is more comprehensively, comprehensive stronger, can save experimental period, high
Effect.
It is described above, any formal limitation not is made to the present invention, although the present invention is disclosed such as by embodiment
On, but the present invention is not limited to, any person skilled in the art, do not departing from technical solution of the present invention scope
It is interior, when the technology contents using the disclosure above make a little change or are modified to the equivalent embodiments of equivalent variations, as long as being
Without departing from the content of technical solution of the present invention, what the technical spirit according to the present invention was made to above example any simply repaiies
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (7)
- A kind of 1. evaluation method for quantitative determining shale intercalator and suppressing clay surface hydration ability, it is characterised in that including with Lower step：S1：Na montmorillonite and intercalator are prepared into intercalation organoclay by stirring, centrifugation, precipitation, drying；S2：Isothermal adsorption is carried out to intercalation clay；S3：Pass through X-ray diffraction method measurement base bottom spacing；S4：Intercalation clay adsorption water type and content are calculated by thermogravimetic analysis (TGA) method；S5：Determine the cation exchange capacity of intercalation clay；S6：Quantitative intercalation clay adsorption water type and content, the degree of hydration of quantitative assessment intercalation clay, accurate measurement intercalation stick Cation exchange capacity, the rejection of quantitative assessment intercalator of soil.
- 2. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, in step S1, na montmorillonite is dried to constant weight under the conditions of 150 DEG C, compound concentration is 1~3% intercalator Solution, the na montmorillonite of a certain amount of drying is added in intercalant solution and stirs 24h, suspension is taken out, import centrifuge tube In, it is filtrated to get sediment；Remaining suspension pours out upper liquid, adds deionized water, is well mixed, 4000rpm's 10min is centrifuged under rotating speed, pours out supernatant, repeats and obtains sediment three times, the sediment obtained twice is true at 80 DEG C Sky is dried, and then in turn through grinding, crosses 200 mesh sieve, constant weight is dried under the conditions of 150 DEG C.
- 3. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, in step S2, adds a certain amount of deionized water in the drier of cleaning, the electrical conductivity of ionized water is 18.25M Ω .cm, inorganic salts are added by the order of different inorganic salts solubility at different temperatures and activity, are put down in 20~30 DEG C of isothermals Weighing apparatus one day, 1g or so na montmorillonite is separately added into measuring cup, its quality is weighed and records, and measuring cup is respectively put into pair In the drier answered, drier lid is covered, isothermal adsorption equilibrium, is taken out with clean paper tape, it is weighed on electronic balance Quality simultaneously records, according to《Several organic slat solution activity and inhibition experimental study》, balance water suction is calculated by formula (1) Amount, formula (1) are as follows：<mrow> <msub> <mi>m</mi> <mi>e</mi> </msub> <mo>=</mo> <mfrac> <mrow> <mo>(</mo> <msub> <mi>m</mi> <mn>2</mn> </msub> <mo>-</mo> <msub> <mi>m</mi> <mn>1</mn> </msub> <mo>)</mo> <mo>-</mo> <mo>(</mo> <msub> <mi>m</mi> <mn>3</mn> </msub> <mo>-</mo> <msub> <mi>m</mi> <mn>0</mn> </msub> <mo>)</mo> </mrow> <mrow> <msub> <mi>m</mi> <mn>1</mn> </msub> <mo>-</mo> <msub> <mi>m</mi> <mn>0</mn> </msub> </mrow> </mfrac> <mo>-</mo> <mo>-</mo> <mo>-</mo> <mrow> <mo>(</mo> <mn>1</mn> <mo>)</mo> </mrow> </mrow>In formula：m0For the quality of measuring cup, g；m1For the quality of measuring cup and na montmorillonite, g；m2After isothermal adsorption equilibrium, claim The quality of measuring bottle and na montmorillonite, g；m3After isothermal adsorption equilibrium, the quality of measuring cup, g.
- 4. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, in step S3, the intercalated montmorillonite of different activity isothermal adsorption equilibriums is taken out, is sealed, open computer, water Cooling system etc., regulation hydraulic pressure flow is more than 3.8L/min；Start main frame, open process of measurement, according to first up voltage, rise electric current again Order, set the voltage and current of work；Set angle of diffraction scope：3 °~40 °, start application program, according to Prague Formula：2dsin θ=n λ, the substrate spacing of intercalation clay is calculated,In formula：N is diffraction progression, here n=1；θ is diffraction half-angle；λ is the wavelength of target, is taken herein
- 5. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, in step S4, sets experiment condition：30~300 DEG C of temperature range；10~30 DEG C/min of heating rate；Protect gas 20mL/min；Purge gas 60mL/min, it is first-order derivative of the TG curves to temperature by DTG curves, and D2TG curves are TG Curve, to the first-order derivative of temperature, determines the step on TG curves, quantitatively distinguishes intercalation to the second derivative of temperature, DTG curves Clay adsorption water type and content, the absorption water content of the different steps calculated by formula (2), formula are as follows：<mrow> <mi>W</mi> <mo>=</mo> <mfrac> <msub> <mi>m</mi> <mrow> <mn>1</mn> <mo>,</mo> <mn>2</mn> </mrow> </msub> <mrow> <mi>m</mi> <mo>-</mo> <msub> <mi>m</mi> <mn>1</mn> </msub> <mo>-</mo> <msub> <mi>m</mi> <mn>2</mn> </msub> </mrow> </mfrac> <mo>&times;</mo> <mn>100</mn> <mo>-</mo> <mo>-</mo> <mo>-</mo> <mrow> <mo>(</mo> <mn>2</mn> <mo>)</mo> </mrow> </mrow>In formula：W is the percentage that the 1st step or the 2nd step adsorpting water quantity account for dry ground quality；m1,2For the 1st step or the 2nd Step adsorpting water quantity, g；M be dry ground and adsorb water gross mass, g.
- 6. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, tells in S5 and inserted according to the measure of professional standard LY/T-1243-1999 forest soil cation exchange capacity (CEC)s, measure Layer clay, the cation exchange capacity CEC values calculated by formula (3), formula are as follows：<mrow> <mi>C</mi> <mi>E</mi> <mi>C</mi> <mo>=</mo> <mfrac> <mrow> <mi>c</mi> <mo>&times;</mo> <mrow> <mo>(</mo> <mi>V</mi> <mo>-</mo> <msub> <mi>V</mi> <mn>0</mn> </msub> <mo>)</mo> </mrow> </mrow> <msub> <mi>m</mi> <mn>1</mn> </msub> </mfrac> <mo>&times;</mo> <mn>100</mn> <mo>-</mo> <mo>-</mo> <mo>-</mo> <mrow> <mo>(</mo> <mn>3</mn> <mo>)</mo> </mrow> </mrow>In formula：CEC is cation exchange capacity, mmol/100g；C be hydrochloric acid standard solution concentration, mol/L；V is salt acidity scale The dosage of quasi- solution, mL；V0For the dosage of blank test hydrochloric acid standard solution, mL；m1For drying sample quality, g.
- 7. quantitative determination shale intercalator according to claim 1 suppresses the evaluation method of clay surface hydration ability, its It is characterised by, tells in S6 by the quantitative intercalation clay adsorption water type of experimental data and content, quantitative assessment intercalation clay Degree of hydration, the cation exchange capacity of accurate measurement intercalation clay, the rejection of quantitative assessment intercalator.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109724894A (en) * | 2018-12-29 | 2019-05-07 | 西南石油大学 | A kind of evaluation method of quantitatively characterizing mud shale water sucting degree |
| WO2019153239A1 (en) * | 2018-02-07 | 2019-08-15 | 西南石油大学 | Drilling fluid for inhibiting clay surface hydration and preparation method therefor |
| CN110231452A (en) * | 2019-05-23 | 2019-09-13 | 武汉大学 | The method for predicting soil clay particle content or salt content based on adsorption isothermal curve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104297096A (en) * | 2014-09-26 | 2015-01-21 | 西南石油大学 | Method for quantitatively determining content of bound water of clay |
| CN105541643A (en) * | 2016-01-13 | 2016-05-04 | 西南石油大学 | Preparation method of polymerizable organic amine cation shale hydration inhibitor |
| CN105733316A (en) * | 2016-01-27 | 2016-07-06 | 北京理工大学 | Preparation method of organic acid salt intercalated modified montmorillonite |
-
2017
- 2017-08-03 CN CN201710655063.4A patent/CN107505432A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104297096A (en) * | 2014-09-26 | 2015-01-21 | 西南石油大学 | Method for quantitatively determining content of bound water of clay |
| CN105541643A (en) * | 2016-01-13 | 2016-05-04 | 西南石油大学 | Preparation method of polymerizable organic amine cation shale hydration inhibitor |
| CN105733316A (en) * | 2016-01-27 | 2016-07-06 | 北京理工大学 | Preparation method of organic acid salt intercalated modified montmorillonite |
Non-Patent Citations (10)
| Title |
|---|
| GANG XIE等: "Intercalation behavior of branched polyethyleneimine into sodium bentonite and its effect on rheological properties", 《APPLIED CLAY SCIENCE》 * |
| GANG XIE等: "Investigation of the inhibition mechanism of the number of primary amine groups of alkylamines on the swelling of bentonite", 《APPLIED CLAY SCIENCE》 * |
| HANYI ZHONG等: "Poly (oxypropylene)-amidoamine modified bentonite as potential shale inhibitor in water-based drilling fluids", 《APPLIED CLAY SCIENCE》 * |
| 何宏平: "《粘土矿物与金属离子作用研究》", 31 January 2001, 石油工业出版社 * |
| 刘向君等: "钻井液浸泡对库车组泥岩强度的影响及应用研究", 《岩石力学与工程学报》 * |
| 宋碧涛等: "聚醚多元醇抑制膨润土水化作用机理研究", 《复杂油气藏》 * |
| 李芳等: "几种有机盐溶液活度及抑制性实验研究", 《西南石油大学学报（自然科学版）》 * |
| 江曙等: "金云母结构修饰及有机改性实验", 《矿物学报》 * |
| 王平全: "粘土表面结合水定量分析及水合机制研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 谢刚等: "黏土结合水的热分析定量研究方法", 《钻井液与完井液》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019153239A1 (en) * | 2018-02-07 | 2019-08-15 | 西南石油大学 | Drilling fluid for inhibiting clay surface hydration and preparation method therefor |
| CN109724894A (en) * | 2018-12-29 | 2019-05-07 | 西南石油大学 | A kind of evaluation method of quantitatively characterizing mud shale water sucting degree |
| CN109724894B (en) * | 2018-12-29 | 2021-07-06 | 西南石油大学 | Evaluation method for quantitatively characterizing water absorption degree of shale |
| CN110231452A (en) * | 2019-05-23 | 2019-09-13 | 武汉大学 | The method for predicting soil clay particle content or salt content based on adsorption isothermal curve |
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