CN104713803B - Method for accurately measuring absorbed phase density of methane on shale - Google Patents

Method for accurately measuring absorbed phase density of methane on shale Download PDF

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CN104713803B
CN104713803B CN201510114441.9A CN201510114441A CN104713803B CN 104713803 B CN104713803 B CN 104713803B CN 201510114441 A CN201510114441 A CN 201510114441A CN 104713803 B CN104713803 B CN 104713803B
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cell
sample
methane
adsorption
helium
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CN104713803A (en
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陈国辉
卢双舫
张光武
李进步
田善思
李吉君
陈方文
王民
薛海涛
王新
田伟超
梁宏儒
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中国石油大学(华东)
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Abstract

The invention relates to a method for accurately measuring absorbed phase density of methane on shale. The method comprises the following steps: 1) smashing a piece of shale sample to be 60-80 meshes, and dividing the powder into two; 2) performing a volumetric method isothermal adsorption experiment on the first shale sample, and obtaining a calculation model of the amount of the adsorbed state methane substance; 3) performing a weight method isothermal adsorption experiment on the second shale sample, and obtaining a calculation model of the mass of the adsorbed state methane; 4) performing adsorbed phase volume correction on the calculation model of the amount of the adsorbed state methane substance, obtained in the step 2) and the calculation model of the mass of the adsorbed state methane, obtained in the step 3), so as to obtain the corrected substance amount calculation model and the corrected mass calculation model of the adsorbed state methane; 5) according to a definition formula of the amount of substance, determining the mass and the volume of the adsorbed state methane; 6) according to the definition of the density, determining an exact value of the adsorbed phase density of methane on the shale.

Description

A kind of accurate measurement methane adsorbs the method for phase density on shale

Technical field

The present invention relates to a kind of method that accurate measurement methane adsorbs phase density on shale, belongs to geological exploration techniques neck Domain.

Background technology

Chinese scholars are inhaled using volumetric method isothermal mostly when the absorption property to coal measures mud stone and shale is studied Attached instrument, in recent years with shale gas exploration and development flourish, gravimetric method isothermal adsorption instrument is also just gradually by Chinese scholars Received, the latter is with magnetic suspension balance as the instrument that predominantly detects, and test result is more accurate.

Chinese scholars are found when being studied coal measures mud stone and shale isothermal adsorption characteristics using volumetric method, in profit When being tested shale adsorbed methane with volumetric method, the presence for adsorbing phase volume will reduce the body of free gass in sample cell Product, and then impact is produced on the test result of shale absorbability.And absorption phase is have ignored in correlational study before this Volume is present, and this will cause for the evaluation of absorbability has relatively large deviation.For such problem, a part of scholar's examination From different angles correction adsorbs phase volume to the impact produced by adsorbed gas aptitude tests to figure.But it is no matter right in which way Impact produced by absorption phase volume is corrected, and substance conservation principle is followed at last, therefore it is nothing to adsorb the determination of phase density The problem that method is avoided, and the accuracy of absorption phase density will directly affect correction result.

Because the research at present for adsorption isotherm experiment adopts volumetric method isothermal adsorption instrument, gravimetric method isothermal adsorption mostly The use of instrument is relatively fewer, and the unification of means of testing leads to not accurately be tested from experimental viewpoint to adsorbing phase density, Therefore, at present both at home and abroad for the research of absorption phase density is still in theory hypothesis and mathematics optimizing phase.Yee D.(1994) Think when temperature is higher than critical temperature (under normal circumstances), to adsorb the limiting density that phase density is equal to gas compression, pushed away with this It is 0.375g/cm by the absorption phase density of methane3.Arri (1992) assumes that absorption phase density is close for the liquid under atmospheric boiling point Degree, the absorption phase density with this inference methane is as 0.421g/cm3.Katsuyuki Murayta (2001) are obtained using empirical equation It is about 0.59g/cm to methane adsorption phase density3.Research above will adsorb phase density as definite value, not consider temperature, pressure Etc. the impact that condition is produced, for this purpose, German scholar Berhard M.Krooss and its team (2008,2010,2012,2013, 2014) Gibbs is combined with regard to the definition adsorbed with langmuir equation, using absorption phase density as undetermined parameter, from mathematics Absorption phase density of the optimization angle to methane and carbon dioxide on coal measures mud stone and shale is evaluated, and obtains different adsorbents With absorption phase density of the adsorbate combination under condition of different temperatures.Similar, domestic scholars Zhou Li (2000,2001) will Gibbs in combination with D-A equations, derives absolute adsorption amount model, and optimization condition of different temperatures to the definition for adsorbing Absorption phase density of the lower methane on AX-21 activated carbons, temperature methane adsorption phase density in 233K-333K is 0.15g/cm3- 0.350g/cm3.This method being optimized in combination with isotherm adsorption model and then to absorption phase density, it is to adsorbing phase The accuracy of density evaluation result will be largely dependent upon the suitability of isotherm adsorption model, and shale pore structure is multiple Miscellaneous, the suitability of isotherm adsorption model is difficult to determine, waits further to grind hence with the evaluation result obtained by the method Study carefully.

To sum up, forefathers are to adsorbing the research of phase density still in theory hypothesis or mathematical optimization stage, not yet from experiment angle Degree is accurately tested it, and different researchers result of study differs greatly, and eventually without final conclusion, this will adsorb to objective evaluation rock Gas ability produces considerable influence.

The content of the invention

For the problems referred to above, it is an object of the invention to provide it is a kind of based on laboratory facilities and strong applicability accurate measurement first Alkane adsorbs the method for phase density on shale.

For achieving the above object, the present invention is employed the following technical solutions:A kind of accurate measurement methane adsorbs phase on shale The method of density, comprises the following steps:1) one piece of mud shale sample comminution is divided into two parts to 60~80 mesh;2) to first part Mud shale sample carries out volumetric method adsorption isotherm experiment, and obtains amount n of the material of ADSORPTION STATE methaneAbsorption CH4Computation model;3) Gravimetric method adsorption isotherm experiment is carried out to second part of mud shale sample, and obtains quality m of ADSORPTION STATE methaneAbsorption CH4Calculating mould Type;4) to step 2) in resulting ADSORPTION STATE methane material amount nAbsorption CH4Computation model and step 3) in it is resulting Quality m of ADSORPTION STATE methaneAbsorption CH4Computation model carry out adsorb phase volume amendment, obtain the revised of ADSORPTION STATE methane The computation model of the amount of material and the computation model of quality;5) according to the defined formula of the amount of material, with reference to step 4) in two Individual computation model, obtains quality m of ADSORPTION STATE methaneAbsorption CH4With volume VAbsorption;6) according to the definition of density, methane is tried to achieve in shale Upper absorption phase density ρAbsorptionExact value, i.e.,:

The step 2) in, amount n of the material of ADSORPTION STATE methane is set up by volumetric method adsorption isotherm experimentAbsorption CH4Meter The process for calculating model is as follows:

1. arranging one includes reference cell, sample cell, the first valve, the second valve, the first thermobarometer, the second thermobarometer, helium The volumetric method isothermal adsorption instrument of gas source of the gas and methane source of the gas, wherein, reference cell connects respectively an air inlet pipeline and an outlet pipe First valve is arranged on air inlet pipeline, and the second valve is arranged on outlet pipe, the end connection sample cell of outlet pipe;The One thermobarometer is arranged in reference cell, and the second thermobarometer is arranged in sample cell;Helium source of the gas and methane source of the gas pass through pipeline It is connected to the initial end of air inlet pipeline;2. it is put into system evacuation in sample cell after first part of mud shale sample, closes the Two valves, then open the first valve, and a certain amount of helium is filled with reference cell using helium source of the gas, and the first valve is closed afterwards Door, after the temperature and pressure of reference cell is stable, records temperature T of helium in reference cellReference cell HeWith pressure PReference cell HeValue, root According to the equation of gas state, have:

PReference cell HeVReference cell=ZReference cell HenReference cell HeRTReference cell He

In above formula, VReference cellFor the volume of reference cell;ZReference cell HeFor the school of the imperfect gas shape body equation of helium in reference cell Positive divisor;nReference cell HeThe amount of the material of helium to be filled with reference cell;R is ideal gas constant;

3. the second valve is opened, the helium in reference cell enters sample cell by outlet pipe, treats reference cell and sample cell Temperature and pressure it is stable after, record temperature T of helium in the system that reference cell is constituted with sample cellSystem HeAnd pressure PSystem HeValue, now, according to the equation of gas state, have:

PSystem HeVSystem freedom=ZSystem HenSystem HeRTSystem He

In above formula, VSystemThe resulting free sky of system after volume and deduction sample volume for reference cell 1 and sample cell 2 Between volume;ZSystem HeIn the system being made up of reference cell 1 and sample cell 2 correction of the imperfect gas shape body equation of helium because Son;nSystem HeFor the summation of the amount of the material of the helium in reference cell 1 and sample cell 2;

4. according to mass conservation law, open the helium content before the second valve in reference cell and be equal to the second valve of opening Helium total content in later reference cell and sample cell, i.e.,:

nReference cell He=nSystem He

By step 2. and 3. in resulting equation substitute into above formula, obtain

5. by step, 4. gained formula tries to achieve volume V of system free spaceSystem freedom

6. again to system evacuation, then by the second valve closing, the first valve is opened, using methane source of the gas to ginseng Than being filled with a certain amount of methane in pond, the first valve is closed afterwards, after the temperature and pressure of reference cell is stable, record reference cell Temperature T of middle methaneReference cell CH4With pressure PReference cell CH4Value, according to the equation of gas state, have:

PReference cell CH4VReference cell=ZReference cell CH4nReference cell CH4RTReference cell CH4

In above formula, ZReference cell CH4For the correction factor of the imperfect gas shape body equation of methane in reference cell;nReference cell CH4To fill Enter the amount of the material of methane in reference cell;

7. the second valve is opened, the methane in reference cell enters sample cell by outlet pipe, treats reference cell and sample cell Temperature and pressure it is stable after, record temperature T of methane in the system that reference cell is constituted with sample cellSystem CH4And pressure PSystem CH4Value, now, according to the equation of gas state, have:

PSystem CH4VSystem freedom=ZSystem CH4nThe free CH4 of systemRTSystem CH4

In above formula, ZSystem CH4The imperfect gas shape body equation of methane in the system being made up of reference cell and sample cell Correction factor;nThe free CH4 of systemFor the amount of the material of the methane of system free space.

8. according to mass conservation law, open the methane content before the second valve in reference cell 1 and be equal to the second valve of opening The methane content of methane content and ADSORPTION STATE after door in system free space, i.e.,:

nReference cell CH4=nThe free CH4 of system+nAbsorption CH4

In above formula, nAbsorption CH4For the amount of the material of the methane of ADSORPTION STATE;

9. by step 6. and 7. in resulting equation substitute into step 8. in the formula of gained, obtain the thing of ADSORPTION STATE methane Amount n of matterAbsorption CH4Computation model:

V in formulaSystem freedom5. it is calculated by step.

The step 3) in, quality m of ADSORPTION STATE methane is set up by gravimetric method adsorption isotherm experimentAbsorption CH4Calculating mould The process of type is as follows:

1. one gravimetric method isothermal adsorption instrument is set, and the top of the adsorption instrument is a magnetic suspension balance, and bottom is one closed Housing, the suspended end in housing installs a sample cylinder, and a float is provided with above sample cylinder;The adsorption instrument is provided with two Gear, when the first gear is placed in, balance weighs the weight of sample cylinder, and balance registration is equal to the weight of sample cylinder and deducts gas pair The buoyancy of sample cylinder;When the second gear is placed in, balance weighs the weight of float and sample cylinder, and balance registration is equal to sample cylinder Weight deducts the buoyancy suffered by sample cylinder and float with the weight sum of float;Further, adsorption instrument is in the second gear Balance registration is subtracted each other with the balance registration in the first gear, that is, obtain between the buoyancy suffered by the weight and float of float Difference;

2. nitrogen is filled with into housing, is then measured under air pressure conditions a and b respectively, measurement meets following relation Formula:

mR1 floats=mFloat-VFloatρ1

mR2 floats=mFloat-VFloatρ2

mR1=mEmpty barrel-VEmpty barrelρ1

mR2=mEmpty barrel-VEmpty barrelρ2

In above formula, mR1 floatsFor nitrogen pressure be a, adsorption instrument be in the second gear when balance registration be in the first gear When balance registration difference;mR2 floatsFor nitrogen pressure be b, adsorption instrument be in the second gear when balance registration be in first grade The difference of balance registration during position;mFloatFor quality;VFloatFor the volume of float;ρ1For density of the nitrogen when air pressure is a;ρ2For Density of the nitrogen when air pressure is b;mR1For nitrogen pressure be a, adsorption instrument be in the first gear when balance registration;mR2For nitrogen Balance registration when gas air pressure is b, adsorption instrument is in the first gear;mEmpty barrelFor the quality of sample cylinder;VEmpty barrelFor the volume of sample cylinder;

Density p of the nitrogen under air pressure conditions a and b is tried to achieve by the first two equation1And ρ2Afterwards, latter two equation is substituted into, is tried to achieve Quality m of sample cylinderEmpty barrelWith volume VEmpty barrel

3. second part of mud shale sample is put into into sample cylinder, then space in housing is heated successively and evacuation at Reason, is then filled with helium into housing, and measures under air pressure conditions c and d respectively, and measurement process meets relational expression:

mR3 floats=mFloat-VFloatρ3

mR4 floats=mFloat-VFloatρ4

mR3=mEmpty barrel+mSample-(VEmpty barrel+VSample3

mR4=mEmpty barrel+mSample-(VEmpty barrel+VSample4

In above formula, mR3 floatsFor helium air pressure be c, adsorption instrument be in the second gear when balance registration be in the first gear When balance registration difference;mR4 floatsFor helium air pressure be d, adsorption instrument be in the second gear when balance registration be in first grade The difference of balance registration during position;ρ3For density of the helium when air pressure is c;ρ4For density of the helium when air pressure is d;mR3For helium Balance registration when gas air pressure is c, adsorption instrument is in the first gear;mR4For helium air pressure be d, adsorption instrument be in the first gear when Balance registration;mSampleFor the quality of second part of mud shale sample;VSampleFor the volume of second part of mud shale sample;

Density p of the helium when air pressure is c and d is tried to achieve by the first two equation3And ρ4After substitute into latter two equation, try to achieve Quality m of two parts of mud shale samplesSampleWith volume VSample

4. again then the space evacuation in housing is filled with into a certain amount of methane into housing, and is measured, surveyed Amount meets relational expression:

mR floats=mFloat-VFloatρ

mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample

In above formula, mR floatsFor current methane gas pressure, adsorption instrument be in the second gear when balance registration be in first The difference of balance registration during gear;ρ is density of the methane under current gas pressure;mRIt is in for the pressure of current methane gas, adsorption instrument Balance registration during the first gear;mAbsorption CH4For the quality of ADSORPTION STATE methane in second part of mud shale sample;

The density p of methane is calculated by previous formula, quality m that latter formula obtains ADSORPTION STATE methane is substituted intoAbsorption CH4

The step 4) in, carry out adsorbing amount n of the material of the ADSORPTION STATE methane of gained after phase volume amendmentAbsorption CH4And matter Amount mAbsorption CH4Computation model be:

mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample+VAbsorption)ρ。

Due to taking above technical scheme, it has advantages below to the present invention:1st, the present invention divides in one piece of mud shale sample Into two parts, a copy of it obtains the computation model of the amount of ADSORPTION STATE methane material by volumetric method adsorption isotherm experiment, another The computation model of the quality of ADSORPTION STATE methane is obtained by gravimetric method adsorption isotherm experiment, two model simultaneous solutions are finally obtained Obtain the precise measurements that methane adsorbs phase density on shale.2nd, amount and quality difference of the present invention to the material of ADSORPTION STATE methane Carry out adsorbing the amendment of phase volume, therefore computation model is more true and reliable so that the result that final survey calculation is obtained is more Plus accurately.3rd, the present invention is measured using experimental technique to the absorption phase density of methane, therefore the strong applicability of the method.

Description of the drawings

Fig. 1 is the structural representation of volumetric method isothermal adsorption instrument of the present invention;

Fig. 2 be gravimetric method isothermal adsorption instrument of the present invention be in the first gear when structural representation;

Fig. 3 be gravimetric method isothermal adsorption instrument of the present invention be in the second gear when structural representation.

Specific embodiment

The present invention is described in detail with reference to the accompanying drawings and examples.

The present invention proposes a kind of method that accurate test methane adsorbs phase density on shale, and it is comprised the following steps:

1) one piece of mud shale sample comminution is divided into two parts to 60~80 mesh.

2) volumetric method adsorption isotherm experiment is carried out to first part of mud shale sample, and obtains the content (first of ADSORPTION STATE methane Amount n of the material of alkaneAbsorption CH4) computation model, detailed process is as follows:

1. as shown in figure 1, arranging one includes reference cell 1, sample cell 2, the first valve 3, the second valve 4, the first thermobarometer 5th, the volumetric method isothermal adsorption instrument of the second thermobarometer 6, helium source of the gas 7 and methane source of the gas 8, wherein, reference cell 1 connects respectively one and enters The outlet pipe 10 of air pipe 9 and, the first valve 3 is arranged on air inlet pipeline 9, and the second valve is arranged on outlet pipe 10, The end connection sample cell 2 of outlet pipe 10;First thermobarometer 5 is arranged in reference cell 1, and the second thermobarometer 6 is arranged on sample In pond 2;Helium source of the gas 7 and methane source of the gas 8 are connected to the initial end of air inlet pipeline 9 by pipeline.

2. it is put into system evacuation in sample cell 2 after first part of mud shale sample, closes the second valve 4, then beats The first valve 3 is opened, a certain amount of helium is filled with reference cell 1 using helium source of the gas, the first valve 3 is closed afterwards, treat reference After the temperature and pressure in pond 1 is stable, temperature T of helium in reference cell 1 is recordedReference cell HeWith pressure PReference cell HeValue.According to gas shape State equation, has:

PReference cell HeVReference cell=ZReference cell HenReference cell HeRTReference cell He (1)

In above formula, VReference cellFor the volume of reference cell 1;ZReference cell HeFor the imperfect gas shape body equation of helium in reference cell 1 Correction factor;nReference cell HeThe amount of the material of helium to be filled with reference cell 1;R is ideal gas constant.

3. the second valve 4 is opened, the helium in reference cell 1 enters sample cell 2, treats the He of reference cell 1 by outlet pipe 10 After the temperature and pressure of sample cell 2 is stablized, temperature T of helium in the system that reference cell 1 is constituted with sample cell 2 is recordedSystem He With pressure PSystem HeValue.Now, according to the equation of gas state, have:

PSystem HeVSystem freedom=ZSystem HenSystem HeRTSystem He (2)

In above formula, VSystemThe resulting free sky of system after volume and deduction sample volume for reference cell 1 and sample cell 2 Between volume;ZSystem HeIn the system being made up of reference cell 1 and sample cell 2 correction of the imperfect gas shape body equation of helium because Son;nSystem HeFor the summation of the amount of the material of the helium in reference cell 1 and sample cell 2.

4. according to mass conservation law, that is, open the helium content before the second valve 4 in reference cell 1 and be equal to opening second Helium total content after valve 4 in reference cell 1 and sample cell 2, can obtain:

nReference cell He=nSystem He (3)

Formula (1), formula (2) are substituted into into formula (3), is had

5. volume V of system free space can be tried to achieve by formula (4)System freedom

6. then the second valve 4 is closed by system evacuation again, the first valve 3 is opened, using methane source of the gas to A certain amount of methane is filled with reference cell 1, the first valve 3 is closed afterwards, after the temperature and pressure of reference cell 1 is stable, record Temperature T of methane in reference cell 1Reference cell CH4With pressure PReference cell CH4Value.According to the equation of gas state, have:

PReference cell CH4VReference cell=ZReference cell CH4nReference cell CH4RTReference cell CH4 (5)

In above formula, ZReference cell CH4For the correction factor of the imperfect gas shape body equation of methane in reference cell 1;nReference cell CH4To fill Enter the amount of the material of methane in reference cell 1.

7. the second valve 4 is opened, the methane in reference cell 1 enters sample cell 2, treats the He of reference cell 1 by outlet pipe 10 After the temperature and pressure of sample cell 2 is stablized, temperature T of methane in the system that reference cell 1 is constituted with sample cell 2 is recordedSystem CH4 With pressure PSystem CH4Value.Now, according to the equation of gas state, have:

PSystem CH4VSystem freedom=ZSystem CH4nThe free CH4 of systemRTSystem CH4 (6)

In above formula, ZSystem CH4The imperfect gas shape body equation of methane in the system being made up of reference cell 1 and sample cell 2 Correction factor;nThe free CH4 of systemFor the amount of the material of the methane of system free space.

8. according to mass conservation law, that is, open the methane content before the second valve 4 in reference cell 1 and be equal to opening second Methane content after valve 4 in system free space and the methane content of ADSORPTION STATE, can obtain:

nReference cell CH4=nThe free CH4 of system+nAbsorption CH4 (7)

In above formula, nAbsorption CH4For the amount of the material of the methane of ADSORPTION STATE.

9. formula (5), formula (6) are substituted into into formula (7), can be obtained:

Formula (8) is the computation model of the amount of the material of ADSORPTION STATE methane, V thereinSystem freedom5. it is calculated by step.

3) gravimetric method adsorption isotherm experiment is carried out to second part of mud shale sample, and obtains the quality of ADSORPTION STATE methane mAbsorption CH4Computation model, detailed process is as follows:

One gravimetric method isothermal adsorption instrument (as shown in Figure 2 and Figure 3) is 1. set, and the top of the adsorption instrument is a magnetic suspension balance 11, bottom is a closed housing 12, and the suspended end in housing 12 installs a sample cylinder 13, is arranged in the top of sample cylinder 13 There is a float 14.The adsorption instrument has two gears to put, and when the first gear is placed in (as shown in Figure 2), balance weighs sample cylinder 13 Weight, balance registration be equal to sample cylinder 13 weight deduct buoyancy of the gas to sample cylinder 13;When the second gear is placed in (such as Shown in Fig. 3), balance weighs the weight of float 14 and sample cylinder 13, and balance registration is equal to the weight and float 14 of sample cylinder 13 Weight sum deducts sample cylinder 13 and the buoyancy suffered by float 14.So further, balance of the adsorption instrument in the second gear shows Number subtracts each other with the balance registration in the first gear, you can to obtain between the buoyancy suffered by the weight and float 14 of float 14 Difference.

2. nitrogen is filled with into housing 12, then measures under air pressure conditions a and b respectively and (control being filled with for nitrogen Amount can change air pressure conditions), the measurement meets relational expression:

mR1 floats=mFloat-VFloatρ1 (9)

mR2 floats=mFloat-VFloatρ2 (10)

mR1=mEmpty barrel-VEmpty barrelρ1 (11)

mR2=mEmpty barrel-VEmpty barrelρ2 (12)

In above formula, mR1 floatsFor nitrogen pressure be a, adsorption instrument be in the second gear when balance registration be in the first gear When balance registration difference;mR2 floatsFor nitrogen pressure be b, adsorption instrument be in the second gear when balance registration be in first grade The difference of balance registration during position;mFloatFor the quality of float;VFloatFor the volume of float;ρ1For density of the nitrogen when air pressure is a; ρ2For density of the nitrogen when air pressure is b;mR1For nitrogen pressure be a, adsorption instrument be in the first gear when balance registration;mR2For Balance registration when nitrogen pressure is b, adsorption instrument is in the first gear;mEmpty barrelFor the quality of sample cylinder 13 (vacant);VEmpty barrelFor sample The volume of product cylinder 13.

Density p of the nitrogen under air pressure conditions a and b can be tried to achieve by formula (9), formula (10)1And ρ2;By ρ1And ρ2Substitution formula (11), formula (12) can try to achieve quality m of sample cylinder 13Empty barrelWith volume VEmpty barrel

3. second part of mud shale sample is put into into sample cylinder 13, then space in housing 12 is heated successively (makes sample In the foreign gas that contains discharge) and evacuation process, helium is then filled with into housing, and respectively in air pressure conditions c With measure under d, measurement process meets relational expression:

mR3 floats=mFloat-VFloatρ3 (13)

mR4 floats=mFloat-VFloatρ4 (14)

mR3=mEmpty barrel+mSample-(VEmpty barrel+VSample3 (15)

mR4=mEmpty barrel+mSample-(VEmpty barrel+VSample4 (16)

In above formula, mR3 floatsFor helium air pressure be c, adsorption instrument be in the second gear when balance registration be in the first gear When balance registration difference;mR4 floatsFor helium air pressure be d, adsorption instrument be in the second gear when balance registration be in first grade The difference of balance registration during position;ρ3For density of the helium when air pressure is c;ρ4For density of the helium when air pressure is d;mR3For helium Balance registration when gas air pressure is c, adsorption instrument is in the first gear;mR4For helium air pressure be d, adsorption instrument be in the first gear when Balance registration;mSampleFor the quality of second part of mud shale sample;VSampleFor the volume of second part of mud shale sample.

By formula (13), formula (14) can in the hope of helium air pressure be c and d when density p3And ρ4;By ρ3And ρ4Substitution formula (15), formula (16) can try to achieve quality m of second part of mud shale sampleSampleWith volume VSample

4. again then the space evacuation in housing 12 is filled with into a certain amount of methane into housing 12, and is surveyed Amount (single pressure condition measurement), measurement meets relational expression:

mR floats=mFloat-VFloatρ (17)

mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample)ρ (18)

In above formula, mR floatsFor current methane gas pressure, adsorption instrument be in the second gear when balance registration be in first The difference of balance registration during gear;ρ is density of the methane under current gas pressure;mRIt is in for the pressure of current methane gas, adsorption instrument Balance registration during the first gear;mAbsorption CH4For the quality of ADSORPTION STATE methane in second part of mud shale sample.

The density p of methane can be obtained by formula (17), ρ is substituted into into formula (18) can obtain the quality of ADSORPTION STATE methane mAbsorption CH4

4) to step 2) in resulting ADSORPTION STATE methane material amount nAbsorption CH4Computation model and step 3) in gained Quality m of the ADSORPTION STATE methane for arrivingAbsorption CH4Computation model carry out adsorb phase volume amendment.For volumetric method, adsorb phase Volume VAbsorptionPresence will occupy sectional interest free volume, it is considered to adsorb phase volume VAbsorptionAfterwards formula (8) translates into formula (19);It is right For gravimetric method, adsorb phase volume VAbsorptionPresence will increase the buoyancy of gas, therefore formula (18) translates into formula (20):

mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample+VAbsorption)ρ (20)

5) according to the definition of the amount of material, have:

mAbsorption CH4=nAbsorption CH4MCH4 (21)

In above formula, MCH4For the molal weight of methane.

Simultaneous equations (19), (20), (21), can try to achieve mAbsorption CH4、nAbsorption CH4And VAbsorption

6) according to the definition of density, methane can be tried to achieve and adsorbs phase density ρ on shaleAbsorptionExact value, i.e.,:

Absorption that can be in the hope of gases such as methane under different experimental conditions on shale using the method for the invention is mutually close Degree, on the basis of each experiment condition is summarized to adsorbing phase density affecting laws, you can obtain the absorption under different experimental conditions Phase density value.Now the test result that adsorption isotherm experiment is carried out individually with volumetric method or gravimetric method can be corrected.

For volumetric method, simultaneous formula (19) (21) and (22) can obtain:

The amount of the material of the ADSORPTION STATE methane after volumetric method correction can be tried to achieve according to formula (23).

And for gravimetric method, simultaneous formula (20) and (22) can obtain:

The present invention is only illustrated with above-described embodiment, and the structure of each part, set location and its connection all can be have Changed, on the basis of technical solution of the present invention, all individual part is carried out improvement according to the principle of the invention and equivalent Conversion, should not exclude outside protection scope of the present invention.

Claims (1)

1. a kind of method that accurate measurement methane adsorbs phase density on shale, comprises the following steps:
1) one piece of mud shale sample comminution is divided into two parts to 60~80 mesh;
2) volumetric method adsorption isotherm experiment is carried out to first part of mud shale sample, and obtains the amount of the material of ADSORPTION STATE methane nAbsorption CH4Computation model;
3) gravimetric method adsorption isotherm experiment is carried out to second part of mud shale sample, and obtains quality m of ADSORPTION STATE methaneAbsorption CH4's Computation model;
4) to step 2) in resulting ADSORPTION STATE methane material amount nAbsorption CH4Computation model and step 3) in it is resulting Quality m of ADSORPTION STATE methaneAbsorption CH4Computation model carry out adsorb phase volume amendment, obtain the revised of ADSORPTION STATE methane The computation model of the amount of material and the computation model of quality;
5) according to the defined formula of the amount of material, with reference to step 4) in the amount of the revised material of ADSORPTION STATE methane that obtains The computation model of computation model and quality, obtains quality m of ADSORPTION STATE methaneAbsorption CH4With volume VAbsorption
6) according to the definition of density, try to achieve methane and adsorb phase density ρ on shaleAbsorptionExact value, i.e.,:
The step 2) in, amount n of the material of ADSORPTION STATE methane is set up by volumetric method adsorption isotherm experimentAbsorption CH4Calculating mould The process of type is as follows:
1. arranging one includes reference cell, sample cell, the first valve, the second valve, the first thermobarometer, the second thermobarometer, helium gas Source and the volumetric method isothermal adsorption instrument of methane source of the gas, wherein, reference cell connects respectively an air inlet pipeline and an outlet pipe, and first Valve is arranged on air inlet pipeline, and the second valve is arranged on outlet pipe, the end connection sample cell of outlet pipe;First is warm Pressure table is arranged in reference cell, and the second thermobarometer is arranged in sample cell;Helium source of the gas and methane source of the gas are connected by pipeline In the initial end of air inlet pipeline;
2. it is put into system evacuation in sample cell after first part of mud shale sample, closes the second valve, then opens first Valve, using helium source of the gas a certain amount of helium is filled with reference cell, and the first valve is closed afterwards, treat reference cell temperature and After pressure stability, temperature T of helium in reference cell is recordedReference cell HeWith pressure PReference cell HeValue, according to the equation of gas state, have:
PReference cell HeVReference cell=ZReference cell HenReference cell HeRTReference cell He
In above formula, VReference cellFor the volume of reference cell;ZReference cell HeFor the non-ideal gas behaviors equation of helium in reference cell correction because Son;nReference cell HeThe amount of the material of helium to be filled with reference cell;R is ideal gas constant;
3. the second valve is opened, the helium in reference cell enters sample cell by outlet pipe, treats the temperature of reference cell and sample cell After degree and pressure are stablized, temperature T of helium in the system that reference cell is constituted with sample cell is recordedSystem HeWith pressure PSystem He's Value, now, according to the equation of gas state, has:
PSystem HeVSystem freedom=ZSystem HenSystem HeRTSystem He
In above formula, VSystem freedomResulting system free space after volume and deduction sample volume for reference cell and sample cell Volume;ZSystem HeThe correction factor of the non-ideal gas behaviors equation of helium in the system being made up of reference cell and sample cell; nSystem HeFor the summation of the amount of the material of the helium in reference cell and sample cell;
4. according to mass conservation law, open the helium content before the second valve in reference cell and be equal to after the second valve of opening Helium total content in reference cell and sample cell, i.e.,:
nReference cell He=nSystem He
By step 2. and 3. in resulting equation substitute into above formula, obtain
5. by step, 4. gained formula tries to achieve volume V of system free spaceSystem freedom
6. again to system evacuation, then by the second valve closing, the first valve is opened, using methane source of the gas to reference cell A certain amount of methane is inside filled with, the first valve is closed afterwards, after the temperature and pressure of reference cell is stable, first in record reference cell Temperature T of alkaneReference cell CH4With pressure PReference cell CH4Value, according to the equation of gas state, have:
PReference cell CH4VReference cell=ZReference cell CH4nReference cell CH4RTReference cell CH4
In above formula, ZReference cell CH4For the correction factor of the non-ideal gas behaviors equation of methane in reference cell;nReference cell CH4To be filled with ginseng Than the amount of the material of the methane in pond;
7. the second valve is opened, the methane in reference cell enters sample cell by outlet pipe, treats the temperature of reference cell and sample cell After degree and pressure are stablized, temperature T of methane in the system that reference cell is constituted with sample cell is recordedSystem CH4With pressure PSystem CH4's Value, now, according to the equation of gas state, has:
PSystem CH4VSystem freedom=ZSystem CH4nThe free CH4 of systemRTSystem CH4
In above formula, ZSystem CH4The correction of the non-ideal gas behaviors equation of methane in the system being made up of reference cell and sample cell The factor;nThe free CH4 of systemFor the amount of the material of the methane of system free space.
8. according to mass conservation law, open the methane content before the second valve in reference cell and be equal to after the second valve of opening The methane content of methane content and ADSORPTION STATE in system free space, i.e.,:
nReference cell CH4=nThe free CH4 of system+nAbsorption CH4
In above formula, nAbsorption CH4For the amount of the material of the methane of ADSORPTION STATE;
9. by step 6. and 7. in resulting equation substitute into step 8. in the formula of gained, obtain the material of ADSORPTION STATE methane Amount nAbsorption CH4Computation model:
V in formulaSystem freedom5. it is calculated by step;
The step 3) in, quality m of ADSORPTION STATE methane is set up by gravimetric method adsorption isotherm experimentAbsorption CH4Computation model Process is as follows:
1. one gravimetric method isothermal adsorption instrument is set, and the top of the adsorption instrument is a magnetic suspension balance, and bottom is a closed housing, Suspended end in housing installs a sample cylinder, and a float is provided with above sample cylinder;The adsorption instrument is provided with two gears, When the first gear is placed in, balance weighs the weight of sample cylinder, and balance registration is equal to the weight of sample cylinder and deducts gas to sample The buoyancy of cylinder;When the second gear is placed in, balance weighs the weight of float and sample cylinder, and balance registration is equal to the weight of sample cylinder The buoyancy suffered by sample cylinder and float is deducted with the weight sum of float;Further, balance of the adsorption instrument in the second gear Registration is subtracted each other with the balance registration in the first gear, that is, obtain the difference between the buoyancy suffered by the weight and float of float;
2. nitrogen is filled with into housing, is then measured under air pressure conditions a and b respectively, measurement meets following relational expression:
mR1 floats=mFloat-VFloatρ1
mR2 floats=mFloat-VFloatρ2
mR1=mEmpty barrel-VEmpty barrelρ1
mR2=mEmpty barrel-VEmpty barrelρ2
In above formula, mR1 floatsFor nitrogen pressure be a, adsorption instrument be in the second gear when balance registration with the first gear when The difference of balance registration;mR2 floatsFor nitrogen pressure be b, adsorption instrument be in the second gear when balance registration with the first gear when Balance registration difference;mFloatFor the quality of float;VFloatFor the volume of float;ρ1For density of the nitrogen when air pressure is a;ρ2For Density of the nitrogen when air pressure is b;mR1For nitrogen pressure be a, adsorption instrument be in the first gear when balance registration;mR2For nitrogen Balance registration when gas air pressure is b, adsorption instrument is in the first gear;mEmpty barrelFor the quality of sample cylinder;VEmpty barrelFor the volume of sample cylinder;
Density p of the nitrogen under air pressure conditions a and b is tried to achieve by the first two equation1And ρ2Afterwards, latter two equation is substituted into, sample is tried to achieve Quality m of cylinderEmpty barrelWith volume VEmpty barrel
3. second part of mud shale sample is put into into sample cylinder, then space in housing is heated successively and evacuation process, so It is filled with helium in backward housing, and measures under air pressure conditions c and d respectively, measurement process meets relational expression:
mR3 floats=mFloat-VFloatρ3
mR4 floats=mFloat-VFloatρ4
mR3=mEmpty barrel+mSample-(VEmpty barrel+VSample3
mR4=mEmpty barrel+mSample-(VEmpty barrel+VSample4
In above formula, mR3 floatsFor helium air pressure be c, adsorption instrument be in the second gear when balance registration with the first gear when The difference of balance registration;mR4 floatsFor helium air pressure be d, adsorption instrument be in the second gear when balance registration with the first gear when Balance registration difference;ρ3For density of the helium when air pressure is c;ρ4For density of the helium when air pressure is d;mR3For helium gas Press for c, adsorption instrument be in the first gear when balance registration;mR4For helium air pressure be d, adsorption instrument be in the first gear when Balance registration;mSampleFor the quality of second part of mud shale sample;VSampleFor the volume of second part of mud shale sample;
Density p of the helium when air pressure is c and d is tried to achieve by the first two equation3And ρ4After substitute into latter two equation, try to achieve second part Quality m of mud shale sampleSampleWith volume VSample
4. again then the space evacuation in housing is filled with into a certain amount of methane into housing, and is measured, measurement is full Sufficient relational expression:
mR floats=mFloat-VFloatρ
mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample
In above formula, mR floatsFor current methane gas pressure, adsorption instrument be in the second gear when balance registration with the first gear when Balance registration difference;ρ is density of the methane under current gas pressure;mRFirst grade is in for the pressure of current methane gas, adsorption instrument Balance registration during position;mAbsorption CH4For the quality of ADSORPTION STATE methane in second part of mud shale sample;
The density p of methane is calculated by previous formula, quality m that latter formula obtains ADSORPTION STATE methane is substituted intoAbsorption CH4
The step 4) in, carry out adsorbing amount n of the material of the ADSORPTION STATE methane of gained after phase volume amendmentAbsorption CH4And quality mAbsorption CH4Computation model be:
mR=mEmpty barrel+mSample+mAbsorption CH4-(VEmpty barrel+VSample+VAbsorption)ρ。
CN201510114441.9A 2015-03-16 2015-03-16 Method for accurately measuring absorbed phase density of methane on shale CN104713803B (en)

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