CN107807143A - The special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate and method - Google Patents
The special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate and method Download PDFInfo
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- CN107807143A CN107807143A CN201711235387.9A CN201711235387A CN107807143A CN 107807143 A CN107807143 A CN 107807143A CN 201711235387 A CN201711235387 A CN 201711235387A CN 107807143 A CN107807143 A CN 107807143A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 31
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- 239000000463 material Substances 0.000 claims description 7
- NUXZAAJDCYMILL-UHFFFAOYSA-K trichlorolanthanum;hydrate Chemical compound O.Cl[La](Cl)Cl NUXZAAJDCYMILL-UHFFFAOYSA-K 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
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Abstract
The present invention discloses a kind of special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate and method, the test system includes low-field nuclear magnetic resonance analyzer, confined pressure cryogenic high pressure is added to pop one's head in, it is not added with confined pressure cryogenic high pressure probe, it is not added with confined pressure normal temperature and pressure probe, temperature confined pressure control module, pore-fluid supplying module and industrial computer, confined pressure cryogenic high pressure is added to pop one's head in by pair, it is not added with confined pressure cryogenic high pressure probe and is not added with confined pressure normal temperature and pressure probe being used in combination and its Curve guide impeller of structure, the measurement signal quantitatively calibrating of low-field nuclear magnetic resonance containing hydrate sediment and the behavior measure of pore scale containing hydrate sediment analysis Study on Integration are realized using mode associated with Multi probe, facilitate the behavioural characteristic research of pore scale containing hydrate sediment, inquire into and lay the foundation for the Parameters variation of Basic Physical Properties containing hydrate sediment micromechanism.
Description
Technical field
The invention belongs to untraditional reservoir engineering and Geotechnical Engineering Basic Physical Properties testing field, is hydrated more particularly to one kind
The special low-field nuclear magnetic resonance Multi probe quantitative testing system of thing and method.
Background technology
Gas hydrates are distributed widely in ocean deepwater ground environment and permafrost ground environment in nature
In, it is richly stored with natural gas, it is considered to be a kind of important potential alternative energy source.Gas hydrate dissociation can weaken
Reservoir intensity and the substantial amounts of potent greenhouse gases of release, it is also considered to be a kind of and induces Geological Hazard and global climate change
The mechanism of change.Therefore, gas hydrates receive the extensive concern of global range, and various countries scientific research personnel is from different perspectives
Substantial amounts of research work is carried out, has carried out gas hydrates runin for several times on this basis and adopted.
However, the gas producing efficiency that ongoing gas hydrates runin is adopted in the world can not meet to be commercialized at this stage
The demand of exploitation, higher requirement is proposed to gas hydrate study work, to the row of pore scale containing hydrate sediment
It is more urgent for the demand of measuring study.Ocean containing hydrate sediment generally by soil particle, gas hydrates, natural gas and
Water forms, and solid phase gas hydrates are filled in deposit interstitial space, reduce the available pore space for being available for flow of fluid,
Change fluid flowing passage spread, cause permeability containing hydrate sediment under the conditions of different hydrate concentrations and
There is obvious difference under different hydrate occurrence forms.Therefore, the pore scale behavior containing hydrate sediment is very
Its Basic Physical Properties Parameters variation is determined in big degree.Nuclear magnetic resonance technique, computed tomography and ESEM
Technology etc. is the conventional means of the measuring behavior of pore scale containing hydrate sediment, and different technologies have different advantage and disadvantage, is fitted
For different study conditions.Nuclear magnetic resonance technique is generally divided into high-field nuclear magnetic resonance technology and low-field nuclear magnetic resonance technology,
The former is limited to due to the untraditional reservoir that is limited in of the factors such as sample size with geotechnical study field there is obvious
Property, and the latter is usually utilized to study the transport property of the porous media materials such as ground.
Under conditions of without gas hydrates, the low-field nuclear magnetic resonance qualitative and quantitative measurement dress of conventional rock-soil material
Put and method is more ripe.However, the more conventional rock-soil material of the behavior of pore scale containing hydrate sediment is increasingly complex, and phase
The measurement experiment answered needs to carry out under low temperature and condition of high voltage, causes the low-field nuclear magnetic resonance such as existing mercury injection method and dehumidification method
Measurement signal quantitatively calibrating method fails, and low-field nuclear magnetic resonance quantitative test technique encounters in gas hydrate study field
Unprecedented challenge, corresponding experimental test procedures and its supporting experiment test system are still more deficient.
The content of the invention
The present invention proposes a kind of Multi probe quantitative testing system of low-field nuclear magnetic resonance containing hydrate and method, using Multi probe
Associated with mode realize the measurement signal quantitatively calibrating of low-field nuclear magnetic resonance containing hydrate sediment and hole containing hydrate sediment
The measurement analysis of gap Scaling behavior, makes up the deficiency in terms of the quantitative test of low-field nuclear magnetic resonance containing hydrate sediment at this stage, is
The Parameters variation of Basic Physical Properties containing hydrate sediment micromechanism is inquired into and laid the foundation.
The present invention is realized using following technical scheme：
A kind of special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate, including industrial computer and be connected with industrial computer
Low-field nuclear magnetic resonance analyzer, temperature confined pressure control module and pore-fluid supplying module, low-field nuclear magnetic resonance analyzer use
To carry out the analysis of NMR relaxation spectrum and imaging analysis to test sample, measuring accuracy is high and speed is fast, and according to actual survey
Examination order is separately installed with low-field nuclear magnetic resonance analyzer to be not added with confined pressure normal temperature and pressure probe, is not added with the spy of confined pressure cryogenic high pressure
Head and plus confined pressure cryogenic high pressure probe, and three probe in be also separately installed with using same processes preparation three parallel surveys
Test agent, size, quality and the porosity all same of three test samples；
The confined pressure normal temperature and pressure probe that is not added with can meet sample test demand under normal temperature and pressure conditionses, including first low
Warm autoclave and first radio-frequency coil supporting with it, the first radio-frequency coil are circumferentially positioned at the first cryogenic high pressure reactor
Outer wall on, designed using split, it is convenient to fill sample regulation；It is not added with confined pressure normal temperature and pressure probe and is directly installed on low-field nuclear magnetic resonance
On analyzer, to realize without hydrate soil sample pore Structure Analysis, sample shape is required without other；
It is described be not added with confined pressure cryogenic high pressure probe can be born in experimentation low temperature needed for gas hydrates and
Condition of high voltage, including the second cryogenic high pressure reactor and second radio-frequency coil supporting with it, the second radio-frequency coil is around setting
On the outer wall of the second cryogenic high pressure reactor, designed using split, it is convenient to fill sample regulation, set in the second cryogenic high pressure reactor
It is equipped with to place the rigid cylinder of test sample, rigid cylinder is ladder shaft-like, including large diameter cylinder and undergauge cylinder, contracting
The end-enclosed of footpath cylinder, the inwall of the outer wall of large diameter cylinder and the second cryogenic high pressure reactor are brought into close contact, undergauge cylinder
Outer wall and the second cryogenic high pressure reactor inwall between form fluorinated oil ring cavity, test sample is arranged in undergauge cylinder；
One end of second cryogenic high pressure reactor is provided with the first end cap, and the other end is provided with the first fluorination oil export and the first fluorinated oil
Entrance, connect to form fluorination by pipeline between the first fluorination oil export and the first fluorination oil-in and temperature confined pressure control module
Oily circulation loop, to fill circularly cooling fluorinated oil to fluorinated oil ring cavity, it can simulate containing hydrate sediment in nature
True temperature condition, gas hydrate system constant total volume in experimentation, be easy to experimental results to analyze, first
The the first pore-fluid entrance connected with undergauge cylinder is additionally provided with end cap, the first pore-fluid entrance passes through pipeline and hole
Fluid supplying module is connected；
Described plus confined pressure cryogenic high pressure probe can bear the low temperature and height needed for gas hydrates in experimentation
Press strip part, including the 3rd cryogenic high pressure reactor and threeth radio-frequency coil supporting with it, the 3rd radio-frequency coil are circumferentially positioned at
On the outer wall of 3rd cryogenic high pressure reactor, designed using split, it is convenient to fill sample regulation, set in the 3rd cryogenic high pressure reactor
There is the sample interstitial space for accommodating test sample, the both ends of the 3rd cryogenic high pressure reactor are divided by end cap seal, and at both ends
The second pore-fluid entrance and the second pore-fluid is not set to export, sample interstitial space and the 3rd cryogenic high pressure reactor inwall
Between be fluorinated oil toroidal cavity, the second fluorination oil-in and are also respectively provided with the 3rd cryogenic high pressure reactor outer wall
Bifluoride oil export, and in test sample flexible membrane is wrapped with to isolate sample interstitial space and fluorinated oil toroidal cavity and have
Effect transmits sample confined pressure；Second pore-fluid entrance and Second gap fluid issuing pass through pipeline and pore-fluid supplying module phase
Company forms fluid circulation loop, and the second fluorination oil-in and the second fluorination oil export pass through pipeline and temperature confined pressure control module
Form low temperature fluorate oil circulation loop.
Further, the temperature confined pressure control module couples control mode using sample temperature with sample confined pressure, including
Refrigeration machine insulating box, low-temperature circulating pump, low temperature fluorate oil vessel, confined pressure load pump and normal temperature fluorination oil vessel, low-temperature circulating pump
It is arranged in refrigeration machine insulating box, one end of low-temperature circulating pump is connected with low temperature fluorate oil vessel, and the other end is loaded by confined pressure
Pump connection normal temperature fluorination oil vessel；
When being not added with confined pressure cryogenic high pressure probe in installation on low-field nuclear magnetic resonance analyzer, the first fluorinated oil arrival end leads to
The connection end that pipeline is crossed with low-temperature circulating pump and confined pressure load pump is connected, and the first fluorinated oil port of export passes through pipeline and low temperature fluorate
Oil vessel is connected；
When in installation on low-field nuclear magnetic resonance analyzer plus confined pressure cryogenic high pressure probe, the second fluorinated oil arrival end passes through
Pipeline is connected with the connection end of low-temperature circulating pump and confined pressure load pump, and the second fluorinated oil port of export passes through pipeline and low temperature fluorate oil
Container is connected, and normal temperature fluorination oil vessel is connected to low temperature fluorate oil circulation loop through confined pressure load pump, and can apply as needed
Confined pressure, i.e., outside the flexible membrane of package testing sample and add confined pressure cryogenic high pressure inner probe wall between toroidal cavity in fill nothing
The fluorinated oil of nuclear magnetic signal, fluorinated oil are circulated with refrigeration control test specimens product temperature between toroidal cavity and refrigeration machine insulating box
Degree, while confined pressure load pump is set in the circulation loop, test sample confined pressure is transmitted by fluorinated oil, confined pressure applies function can
It is turned on and off according to testing requirement.
Further, the pore-fluid supplying module prepares container including gas cylinder, tank, gas saturation water
And backpressure valve, it is available for different gas hydrates synthetic methods to use, to study synthetic method for being sunk containing hydrate
The affecting laws of product thing pore scale behavior, the tank and gas cylinder pass through connecting line and gas saturation water respectively
Prepare container to be connected, and corresponding switch valve is respectively arranged with connecting line, tank is prepared with gas saturation water to be held
Distilled water injection pump is additionally provided between device, gas saturation water prepares container and is also associated with a circulation constant flow pump, and gas cylinder is
Methane gas cylinder；
When being not added with confined pressure cryogenic high pressure probe in installation on low-field nuclear magnetic resonance analyzer, gas saturation water prepares container
Directly it is connected by circulating constant flow pump with the first pore-fluid entrance；
When in installation on low-field nuclear magnetic resonance analyzer plus confined pressure cryogenic high pressure probe, the second pore-fluid arrival end leads to
Cross pipeline with circulation constant flow pump to be connected, the second pore-fluid port of export is connected to gas saturation water through backpressure valve by pipeline and prepared
Container, pore-fluid supplying module is with adding confined pressure cryogenic high pressure probe to form fluid circulation loop.
Further, the first cryogenic high pressure reactor, the second cryogenic high pressure reactor and the reaction of the 3rd cryogenic high pressure
Kettle is used without nuclear magnetic signal material.
Further, it is described to be not added with being additionally provided with the first TEMP in the fluorinated oil ring cavity of confined pressure cryogenic high pressure probe
Device, add in the fluorinated oil toroidal cavity that confined pressure cryogenic high pressure pops one's head in and be provided with second temperature sensor, the first temperature sensor and
Second temperature sensor and industry control mechatronics.
Further, prepared by the gas saturation water is additionally provided with pressure sensor in container, the pressure sensor with
Industry control mechatronics.
Further, prepared by the gas saturation water is additionally provided with magnetic stirrer in container, to promote gases at high pressure
It is dissolved in water.
Further, the gas cylinder uses methane gas cylinder.
Further, the length of the test sample is 20mm-60mm, and a diameter of 25.4mm, sample length can be according to reality
Test demand regulation.
Based on test system described above, the present invention also proposes that a kind of special low-field nuclear magnetic resonance of hydrate is visited more in addition
Head quantitative measuring method, comprises the following steps：
(1) parallel soil sample is prepared：
Three parallel soil samples are prepared using identical process, i.e. test sample, three soil samples are of the same size, are identical
Quality and identical porosity, ensure three soil samples pore structure be identical in statistical significance；
(2) it is not added with confined pressure normal temperature and pressure probe measurement：Without hydrate soil sample pore Structure Analysis；
Take a soil sample to be positioned over to be not added with confined pressure normal temperature and pressure probe, low field is installed in after distillation saturation soil sample
On magnetic nuclear resonance analyzer, low-field nuclear magnetic resonance analyzer is run, obtains T2 distribution curves, qualitative analysis is hydrated without natural gas
The porosity distribution of thing soil sample and the porosity do not demarcated；
(3) it is not added with confined pressure cryogenic high pressure probe measurement：Quantitatively calibrating, determine transverse relaxation rate；
Take a soil sample to be positioned over again to be not added with confined pressure cryogenic high pressure probe, and connect itself and temperature confined pressure control module
With the annexation of pore-fluid injection module, the synthesizing methane hydrate in soil sample, gas flow conservation method is used during this
Calculated hydration thing saturation degree, i.e., hydrate concentration is calculated according to gas whole synthesizing methane hydrate, at the same time run low
Field nuclear magnetic resonance analyzer obtains the T2 distribution curves containing hydrate sediment, analyzes effective hole of the soil sample containing gas hydrates
Gap distribution characteristics and effecive porosity is not demarcated, not the demarcating without gas hydrates soil sample obtained with reference to step (2)
Porosity calculation hydrate concentration, the hydrate concentration quantitatively calibrating base calculated in conjunction with the gas flow conservation method of this step
In the hydrate concentration that low-field nuclear magnetic resonance T2 distribution curves determine, it is determined that the experiment transverse direction used containing hydrate sediment is relaxed
Henan rate；
(4) confined pressure cryogenic high pressure probe measurement is added：The behavior of qualitative analysis pore scale containing hydrate sediment；
Take remaining soil sample be positioned over plus confined pressure cryogenic high pressure probe in, and connect its with temperature confined pressure control module and
The annexation of pore-fluid injection module, set in the range of 1MPa-10MPa after arbitrary effective confining pressure, using saturation methane
The distillation water circulation of gas prepares method synthesizing methane hydrate in soil sample, control gas saturation water system of then slowly deflating manually
Standby container inner pressure gradually decomposes hydrate, and operation low-field nuclear magnetic resonance analyzer is obtained in lanthanum chloride hydrate and decomposable process not
The T2 distribution curves of test sample in the same time, in conjunction with step (3) determine transverse relaxation rate, quantitative analysis lanthanum chloride hydrate with
The Evolution of the distribution curve of pore radius containing hydrate sediment in decomposable process；
Further, can also be by changing effective confining pressure in step (4), quantitative analysis effective confining pressure is to containing hydration
The affecting laws of sediment pore radius distribution curve.
Compared with prior art, the advantages and positive effects of the present invention are：
1st, the present invention is normal by that will add confined pressure cryogenic high pressure probe, and be not added with confined pressure cryogenic high pressure probe and be not added with confined pressure normal temperature
Pressure probe is used in combination, there is provided a kind of measurement signal quantitatively calibrating method of low-field nuclear magnetic resonance containing hydrate sediment, realizes
Measurement signal demarcation is with sample test analysis integrated；
2nd, plus confined pressure cryogenic high pressure probe can simulate real reservoir stress and temperature conditionss, experimentation in nature
It is middle that real gas hydrates generating process in nature can be simulated using gas saturation water circulation preparation method, it is beneficial to grind
Study carefully the evolution of the pore scale behavior such as pore radius containing natural gas hydrate stratum in Gas Hydrate Deposition and recovery process
Rule；
3rd, it is not added with the rigid cylinder inside confined pressure cryogenic high pressure probe not deform in experimentation, sample body
Product remains constant, is beneficial to by pressure decline method calculated hydration thing saturation degree, and low-field nuclear magnetic resonance letter is carried out as standard
The transverse relaxation rate that number quantitatively calibrating obtains is more accurately and reliably；
4th, it is easy to use to be not added with confined pressure normal temperature and pressure probe, is easily obtained bent without gas hydrates soil sample distribution of pores
Line, basic support data are provided for the follow-up pore scale of soil sample containing gas hydrates performance testing analysis.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 is not added with confined pressure normal temperature and pressure sonde configuration schematic diagram；
Fig. 2 is that the embodiment of the present invention 1 is not added with confined pressure cryogenic high pressure sonde configuration schematic diagram；
Fig. 3 is the embodiment of the present invention 1 plus confined pressure cryogenic high pressure sonde configuration schematic diagram；
Fig. 4 is that the embodiment of the present invention 1 is not added with confined pressure cryogenic high pressure probe and test system connection diagram；
Fig. 5 is the embodiment of the present invention 1 plus confined pressure cryogenic high pressure probe and test system connection diagram；
Fig. 6 is method of testing flow chart described in the embodiment of the present invention 2.
Embodiment
In order to which the above objects, features and advantages of the present invention is more clearly understood, below in conjunction with the accompanying drawings and implement
Example the present invention will be further described, elaborate many details in the following description to facilitate a thorough understanding of the present invention,
But the present invention can also be implemented using different from other modes described here, however it is not limited to following public specific real
Apply example.
Embodiment 1, a kind of special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate, including industrial computer and and work
Control machine connected low-field nuclear magnetic resonance analyzer, temperature confined pressure control module and pore-fluid supplying module, low-field nuclear magnetic resonance
Analyzer composes analysis and imaging analysis to carry out NMR relaxation to test sample, and according to actual test order in low field
Be separately installed with magnetic nuclear resonance analyzer be not added with confined pressure normal temperature and pressure probe, be not added with confined pressure cryogenic high pressure probe with plus confined pressure it is low
Warm high-voltage probe, and the three parallel testing samples prepared using same processes are also separately installed with three probes, three
Size, quality and the porosity all same of test sample, the length of test sample are 20mm-60mm, a diameter of 25.4mm, sample
Length can only have 30mm length according to experiment demand regulation, such as live sample in situ, can also carry the system and measure.
The confined pressure normal temperature and pressure probe that is not added with can meet sample test demand under normal temperature and pressure conditionses, as shown in figure 1,
Including the first cryogenic high pressure reactor 11 and first radio-frequency coil 12 supporting with it, the first radio-frequency coil 12 is circumferentially positioned at
On the outer wall of one cryogenic high pressure reactor 11, designed using split, it is convenient to fill sample regulation；During experiment, confined pressure normal temperature and pressure is not added with
Probe is directly installed on low-field nuclear magnetic resonance analyzer, by low-field nuclear magnetic resonance analyzer to realize no hydrate soil sample hole
Gap structure is analyzed, and the probe is required without other the shape of test sample 1, can to the unconsolidated sediment without gas hydrates and
Consolidation rock core etc. is tested, convenient to provide complete skeleton test data support pore scale containing hydrate sediment behavior point
Analysis, in addition, also facilitating the test of porosity standard specimen to demarcate the reliability of evaluation low-field nuclear magnetic resonance test result.
It is described be not added with confined pressure cryogenic high pressure probe can be born in experimentation low temperature needed for gas hydrates and
Condition of high voltage, with reference to figure 2, including the second cryogenic high pressure reactor 21 and second radio-frequency coil 22 supporting with it, the second radio frequency
Coil encircling 22 is arranged on the outer wall of the second cryogenic high pressure reactor 21, is designed using split, and convenient to fill sample regulation, second is low
It is provided with to place the rigid cylinder of test sample 1 in warm autoclave 21, rigid cylinder is ladder shaft-like, including big straight
Footpath cylinder 23 and undergauge cylinder 34, the end-enclosed of undergauge cylinder 24, the outer wall of large diameter cylinder 23 and the second cryogenic high pressure are anti-
The inwall of kettle 21 is answered to be brought into close contact, and the end face of the end face of large diameter cylinder 23 and the one end of the second cryogenic high pressure reactor 21 is put down
Together, fluorinated oil ring cavity 25 is formed between the inwall of the outer wall of undergauge cylinder 24 and the second cryogenic high pressure reactor, test sample 1 is set
Put in undergauge cylinder 24；One end of second cryogenic high pressure reactor 21 is provided with the first end cap 26, and the other end is provided with first
It is fluorinated oil export 27 and first and is fluorinated oil-in 28, the first fluorination oil export 27 and first is fluorinated oil-in 28 and temperature confined pressure control
Connect to form fluorinated oil circulation loop by pipeline between molding block, to fill circularly cooling fluorinated oil, energy to fluorinated oil ring cavity
Enough simulate the true temperature condition containing hydrate sediment in nature, gas hydrate system cumulative volume in experimentation
It is constant, it is easy to experimental results to analyze, the first pore-fluid connected with undergauge cylinder 24 is additionally provided with the first end cap 26
Entrance 29, the first pore-fluid entrance 29 are connected by pipeline with pore-fluid supplying module；
Described plus confined pressure cryogenic high pressure probe can bear the low temperature and height needed for gas hydrates in experimentation
Press strip part, true temperature and reservoir stress environment in nature containing hydrate sediment can be simulated, makes experiment test knot
Fruit has more referential, with reference to figure 3, including the 3rd cryogenic high pressure reactor 31 and threeth radio-frequency coil 32 supporting with it, the 3rd
Radio-frequency coil 32 is circumferentially positioned on the outer wall of the 3rd cryogenic high pressure reactor 31, is designed using split, and the convenient sample that fills is adjusted, the
The sample interstitial space 33 for accommodating test sample 1, the 3rd cryogenic high pressure reactor 31 are provided with three cryogenic high pressure reactors 31
Both ends by end cap seal, and set at both ends the second pore-fluid entrance 34 and the second pore-fluid to export 35 respectively, sample
It is fluorinated oil toroidal cavity 36 between product interstitial space 33 and the inwall of the 3rd cryogenic high pressure reactor 31, it is anti-in the 3rd cryogenic high pressure
Answer and the second fluorination oil-in 37 and the second fluorination oil export 38 are also respectively provided with the outer wall of kettle 31, and in test sample outer wrapping
Flexible film 39 is to isolate sample interstitial space 33 and fluorinated oil toroidal cavity 36 and effectively transmission sample confined pressure；Second hole stream
Body entrance 34 and Second gap fluid issuing 35 are connected to form fluid circulation loop by pipeline and pore-fluid supplying module, and
Second fluorination oil-in 37 and second is fluorinated oil export 38 and followed by pipeline and temperature confined pressure control module composition low temperature fluorate oil
Loop back path.
In the present embodiment, the temperature confined pressure control module couples control mode using sample temperature with sample confined pressure, such as
Shown in Fig. 4 and Fig. 5, temperature confined pressure control module includes refrigeration machine insulating box 4, low-temperature circulating pump 5, low temperature fluorate oil vessel 6, enclosed
Load pump 7 and normal temperature fluorination oil vessel 8 are pressed, low-temperature circulating pump 5 is arranged in refrigeration machine insulating box 4, one end of low-temperature circulating pump 5
It is connected with low temperature fluorate oil vessel 6, the other end connects normal temperature by confined pressure load pump 7 and is fluorinated oil vessel 8；It is total to when in low field nuclear-magnetism
When installation is not added with confined pressure cryogenic high pressure probe on vibration analysis instrument, with reference to figure 5, the first fluorination end of oil-in 28 passes through pipeline and low temperature
Circulating pump 5 is connected with the connection end of confined pressure load pump 7, and the first fluorination end of oil export 27 passes through pipeline and low temperature fluorate oil vessel 6
It is connected；
When in installation on low-field nuclear magnetic resonance analyzer plus confined pressure cryogenic high pressure probe, with reference to figure 5, the second fluorinated oil enters
37 ends of mouth are connected by pipeline with the connection end of low-temperature circulating pump 5 and confined pressure load pump 7, and the second fluorination oil export 38 end passes through pipe
Road is connected with low temperature fluorate oil vessel 6, and normal temperature fluorination oil vessel 8 is connected to low temperature fluorate oil circulation loop through confined pressure load pump 7,
And confined pressure can be applied as needed, i.e., the flexible membrane 39 in package testing sample is outer and adds between confined pressure cryogenic high pressure inner probe wall
Fluorinated oil toroidal cavity 36 in fill the fluorinated oil of no nuclear magnetic signal, fluorinated oil is between toroidal cavity and refrigeration machine insulating box
Circulation is passed with refrigeration control test sample temperature, while by setting confined pressure load pump 7 in the circulation loop by fluorinated oil
Test sample confined pressure is passed, confined pressure, which applies function, to be turned on and off according to testing requirement.
Temperature voltage stabilizing control module can meet gas hydrates generation for temperature and confined pressure control range and decompose
Required temperature and pressure condition, and innovate by the way of low temperature fluorate oil circulation temperature lowering, can effectively avoid air-cooled side
The problem of sample cell outer absorbent member caused by air compressor and long pipe runs drier needed for formula freezes and influences nuclear magnetic signal；
Grown using without the fluorinated oil that nuclear magnetic signal disturbs as temperature medium, stream time；And the refrigeration of subzero 60 DEG C of ultralow temperature
Machine insulating box can provide stable low-temperature receiver, can reduce sample temperature rapidly and keep stable, sample temperature control range is zero
Lower 20 DEG C are arrived normal temperature, and temperature-controlled precision is 0.1 DEG C；Sample confined pressure, which is applied with, is limited to 20MPa.
With continued reference to Fig. 4 and Fig. 5, the pore-fluid supplying module includes gas cylinder 13, tank 14, gas and satisfied
Container 15 and backpressure valve 16 are prepared with water, is available for different gas hydrates synthetic methods to use, to study synthesis side
For the affecting laws of the behavior of pore scale containing hydrate sediment, the tank 14 and gas cylinder 13 pass through method respectively
Connecting line prepares container 15 with gas saturation water and is connected, and corresponding switch valve, water storage are respectively arranged with connecting line
Container 14 and gas saturation water are additionally provided with distilled water injection pump 17 between preparing container, and gas saturation water prepares container 15 and also connected
A circulation constant flow pump 18 is connected to, prepared by the gas saturation water is additionally provided with magnetic stirrer 19 in container, to promote high pressure
Gas is dissolved in water, adjustable between rotating speed 0-2000rpm；The gas cylinder 13 uses methane gas cylinder, gas saturation water
It is stainless steel to prepare container 15, interior diameter 100mm, a height of 200mm, and its dischargeable capacity is 2261ml, pressure-resistant 25MPa,
Tank is glass material, and dischargeable capacity 1000ml, it is 50ml/min that the circulation infusion of constant current 18, which enters fluid flow rate upper limit, resistance to
Press 25MPa；The control accuracy of backpressure valve 16 is ± 0.1MPa, according to different gas hydrates synthetic methods, uses hole
Different parts in fluid supplying module；
Such as when being not added with confined pressure cryogenic high pressure probe in installation on low-field nuclear magnetic resonance analyzer 10, with reference to figure 4, gas
Body saturation water prepares container 15 and is directly connected by circulating constant flow pump 18 with the first pore-fluid entrance 29；It is total to when in low field nuclear-magnetism
On vibration analysis instrument 10 installation plus confined pressure cryogenic high pressure probe when, as shown in figure 5, the end of the second pore-fluid entrance 34 by pipeline with
Circulate constant flow pump 18 to be connected, the second pore-fluid, which exports 35 ends and is connected to gas saturation water through backpressure valve 16 by pipeline and prepares, to be held
Device 15, pore-fluid supplying module is with adding confined pressure cryogenic high pressure probe to form fluid circulation loop.
In addition, the first cryogenic high pressure reactor 11 described in the present embodiment, the second cryogenic high pressure reactor 21 and the 3rd are low
Warm autoclave 31 is used without nuclear magnetic signal material, and the upper limit that reactor is pressure-resistant is 30MPa, can arrive room temperature bar at subzero 40 DEG C
Normal work under part, and the first temperature sensor A is additionally provided with the fluorinated oil ring cavity 25 for being not added with confined pressure cryogenic high pressure probe,
Add in the fluorinated oil toroidal cavity 36 of confined pressure cryogenic high pressure probe and be provided with second temperature sensor B, the gas saturation water system
Be additionally provided with pressure sensor in standby container 15, the first temperature sensor A and second temperature sensor B and pressure sensor with
Industry control mechatronics, to gather the data such as the temperature in experimentation, pressure.
Low-field nuclear magnetic resonance analyzer and industrial computer described in the present embodiment use the production of Suzhou Niu Mai companies
Existing equipment, such as, low-field nuclear magnetic resonance analyzer can use MesoMR23-060H-I type equipment, and test sample can be entered
The analysis of row NMR relaxation spectrum and imaging analysis, it is primarily used to obtain the T2 T2 data of sample, test essence
Degree is high and speed is fast, the porosity of test sample, pore-size distribution, irreducible water and permeability etc. can be characterized, industry control owner
Realize test system is automatically controlled, data automatic recording and subsequent result analysis etc..
Embodiment 2, based on test system described above, the present invention also proposes a kind of special low field nuclear-magnetism of hydrate in addition
Resonate Multi probe quantitative measuring method, as shown in fig. 6, comprising the following steps：
(1) parallel soil sample is prepared：
Three parallel soil samples are prepared using identical process, i.e. test sample, three soil samples are of the same size, are identical
Quality and identical porosity, ensure three soil samples pore structure be identical in statistical significance；
(2) it is not added with confined pressure normal temperature and pressure probe measurement：Without hydrate soil sample pore Structure Analysis；
Take a soil sample to be positioned over to be not added with confined pressure normal temperature and pressure probe, low field is installed in after distillation saturation soil sample
On magnetic nuclear resonance analyzer, low-field nuclear magnetic resonance analyzer is run, obtains T2 distribution curves, qualitative analysis is hydrated without natural gas
The porosity distribution of thing soil sample and porosity is not demarcated；
(3) it is not added with confined pressure cryogenic high pressure probe measurement：Quantitatively calibrating, determine transverse relaxation rate；
Take a soil sample to be positioned over again to be not added with confined pressure cryogenic high pressure probe, and connect itself and temperature confined pressure control module
With the annexation of pore-fluid injection module, setting volume is injected into soil sample according to the hydrate concentration being fitted to first
Methane gas, then reinjects pure water or salt solution increase soil sample pore pressure, pore pressure gradually drop with lanthanum chloride hydrate
Low, multiple moisturizing supercharging no longer substantially reduces (typically smaller than 0.2MPa) until pore pressure, then it is assumed that all methane gas are equal
Synthesizing methane hydrate, using gas flow conservation method calculated hydration thing saturation degree, i.e., after all equal synthesized hydrates of methane gas
With reference to methane hydrate molecular formula CH4·NhH2O calculated hydration thing saturation degrees；At the same time low-field nuclear magnetic resonance analyzer is run
The T2 distribution curves containing hydrate sediment are obtained, analyze the active porosity distribution characteristics and not of the soil sample containing gas hydrates
Demarcate effecive porosity；
Porosity calculation hydrate concentration is not demarcated without gas hydrates soil sample with reference to what step (2) obtained,
It is bent that the hydrate concentration quantitatively calibrating calculated in conjunction with the gas flow conservation method of this step is based on low-field nuclear magnetic resonance T2 distributions
The hydrate concentration that line determines, it is determined that the experiment transverse relaxation rate used containing hydrate sediment；
(4) confined pressure cryogenic high pressure probe measurement is added：The behavior of qualitative analysis pore scale containing hydrate sediment；
Take remaining soil sample be positioned over plus confined pressure cryogenic high pressure probe in, and connect its with temperature confined pressure control module and
The annexation of pore-fluid injection module, set in the range of 1MPa-10MPa after arbitrary effective confining pressure, using saturation methane
The distillation water circulation of gas prepares method synthesizing methane hydrate in soil sample, and prepared by control gas saturation water of then slowly deflating holds
Pressure gradually decomposes hydrate in device, operation low-field nuclear magnetic resonance analyzer obtain lanthanum chloride hydrate from it is different in decomposable process when
The T2 distribution curves of test sample are carved, the transverse relaxation rate determined with reference to step (3), quantitative analysis lanthanum chloride hydrate was with decomposing
The Evolution of the distribution curve of pore radius containing hydrate sediment in journey；
In addition, change effective confining pressure repeat step (4) in the range of 1MPa-10MPa, it may also be used for quantitative analysis is effectively enclosed
Press the affecting laws to the distribution curve of pore radius containing hydrate sediment.
Realize that the measurement signal of low-field nuclear magnetic resonance containing hydrate sediment is quantitatively marked by using mode associated with Multi probe
It is fixed integrated with the analysis of the behavior measure of pore scale containing hydrate sediment, facilitate the behavior of pore scale containing hydrate sediment
Properties study, inquire into and lay the foundation for the Parameters variation of Basic Physical Properties containing hydrate sediment micromechanism, have extensive practical
And application value.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Effect embodiment is applied to other fields, but every without departing from technical solution of the present invention content, the technical spirit according to the present invention
Any simple modification, equivalent variations and the remodeling made to above example, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. the special low-field nuclear magnetic resonance Multi probe quantitative testing system of hydrate, it is characterised in that including industrial computer and and industry control
Machine connected low-field nuclear magnetic resonance analyzer, temperature confined pressure control module and pore-fluid supplying module, low-field nuclear magnetic resonance point
Analyzer composes analysis and imaging analysis to carry out NMR relaxation to test sample, and according to actual test order in low field core
Installation is not added with confined pressure normal temperature and pressure probe, is not added with confined pressure cryogenic high pressure probe and adds confined pressure low temperature high respectively on magnetic resonance analyzer
Pressure probe, and three test samples prepared using same processes, three test samples are also respectively provided with three probes
Size, quality and porosity all same；
The confined pressure normal temperature and pressure probe that is not added with includes the first cryogenic high pressure reactor and first radio-frequency coil supporting with it, the
One radio-frequency coil is circumferentially positioned on the outer wall of the first cryogenic high pressure reactor, is not added with confined pressure normal temperature and pressure probe and is directly installed on
On low-field nuclear magnetic resonance analyzer, to realize without hydrate soil sample pore Structure Analysis；
The confined pressure cryogenic high pressure probe that is not added with includes the second cryogenic high pressure reactor and second radio-frequency coil supporting with it, the
Two radio-frequency coils are circumferentially positioned on the outer wall of the second cryogenic high pressure reactor, be provided with the second cryogenic high pressure reactor to
The rigid cylinder of test sample is placed, rigid cylinder is ladder shaft-like, including large diameter cylinder and undergauge cylinder, undergauge cylinder
End-enclosed, the inwall of the outer wall of large diameter cylinder and the second cryogenic high pressure reactor are brought into close contact, the outer wall of undergauge cylinder with
Fluorinated oil ring cavity is formed between the inwall of second cryogenic high pressure reactor, test sample is arranged in undergauge cylinder；Second low temperature
One end of autoclave is provided with the first end cap, and the other end is provided with the first fluorination oil export and the first fluorination oil-in, the
Connect to form circulation loop by pipeline between one fluorination oil export and the first fluorination oil-in and temperature confined pressure control module, the
One end covers the first pore-fluid entrance for being additionally provided with and being connected with undergauge cylinder, and the first pore-fluid entrance passes through pipeline and hole
Clearance flow body supplying module is connected；
Described plus confined pressure cryogenic high pressure, which is popped one's head in, includes the 3rd cryogenic high pressure reactor and threeth radio-frequency coil supporting with it, and the 3rd
Radio-frequency coil is circumferentially positioned on the outer wall of the 3rd cryogenic high pressure reactor, and receiving is provided with the 3rd cryogenic high pressure reactor and is surveyed
The sample interstitial space of test agent, the both ends of the 3rd cryogenic high pressure reactor set at both ends respectively by end cap seal
Two pore-fluid entrances and the outlet of the second pore-fluid, are fluorine between sample interstitial space and the 3rd cryogenic high pressure reactor inwall
Carburetion toroidal cavity, the second fluorination oil-in and the second fluorinated oil are also respectively provided with the 3rd cryogenic high pressure reactor outer wall
Outlet, and flexible membrane is wrapped with to isolate sample interstitial space and fluorinated oil toroidal cavity and effectively transmit sample in test sample
Product confined pressure；Second pore-fluid entrance and Second gap fluid issuing are connected to form stream by pipeline and pore-fluid supplying module
Body circulation loop, and the second fluorination oil-in and the second fluorination oil export form low temperature by pipeline and temperature confined pressure control module
Fluorinated oil circulation loop.
2. test system according to claim 1, it is characterised in that：It is permanent that the temperature confined pressure control module includes refrigeration machine
Incubator, low-temperature circulating pump, low temperature fluorate oil vessel, confined pressure load pump and normal temperature fluorination oil vessel, low-temperature circulating pump are arranged on system
In cold insulating box, one end of low-temperature circulating pump is connected with low temperature fluorate oil vessel, and the other end is connected normal by confined pressure load pump
Temperature fluorination oil vessel；
When being not added with confined pressure cryogenic high pressure probe in installation on low-field nuclear magnetic resonance analyzer, the first fluorinated oil arrival end passes through pipe
Road is connected with the connection end of low-temperature circulating pump and confined pressure load pump, and the first fluorinated oil port of export is held by pipeline and low temperature fluorate oil
Device is connected；
When in installation on low-field nuclear magnetic resonance analyzer plus confined pressure cryogenic high pressure probe, the second fluorinated oil arrival end passes through pipeline
It is connected with the connection end of low-temperature circulating pump and confined pressure load pump, the second fluorinated oil port of export passes through pipeline and low temperature fluorate oil vessel
It is connected, normal temperature fluorination oil vessel is connected to low temperature fluorate oil circulation loop through confined pressure load pump.
3. test system according to claim 1 or 2, it is characterised in that：The pore-fluid supplying module includes high pressure
Gas cylinder, tank, gas saturation water prepare container and backpressure valve, and the tank and gas cylinder pass through connection respectively
Pipeline prepares container with gas saturation water and is connected, and corresponding switch valve is respectively arranged with connecting line, tank with
Gas saturation water is additionally provided with distilled water injection pump between preparing container, and gas saturation water prepares container and is also associated with circulation perseverance
Flow pump；
When being not added with confined pressure cryogenic high pressure probe in installation on low-field nuclear magnetic resonance analyzer, gas saturation water prepares container and passed through
Circulation constant flow pump is directly connected with the first pore-fluid entrance；
When in installation on low-field nuclear magnetic resonance analyzer plus confined pressure cryogenic high pressure probe, the second pore-fluid arrival end passes through pipe
Road is connected with circulation constant flow pump, and the second pore-fluid port of export is connected to gas saturation water and prepared by pipeline through backpressure valve to be held
Device, pore-fluid supplying module is with adding confined pressure cryogenic high pressure probe to form fluid circulation loop.
4. test system according to claim 3, it is characterised in that：The first cryogenic high pressure reactor, the second low temperature
Autoclave and the 3rd cryogenic high pressure reactor use to be made without nuclear magnetic signal material.
5. test system according to claim 4, it is characterised in that：The fluorinated oil for being not added with confined pressure cryogenic high pressure probe
The first temperature sensor is additionally provided with ring cavity, adds and the second temperature is provided with the fluorinated oil toroidal cavity of confined pressure cryogenic high pressure probe
Spend sensor, the first temperature sensor and second temperature sensor and industry control mechatronics.
6. test system according to claim 5, it is characterised in that：The gas saturation water, which is prepared in container, to be additionally provided with
Pressure sensor, the pressure sensor and industry control mechatronics.
7. test system according to claim 6, it is characterised in that：The gas saturation water, which is prepared in container, to be additionally provided with
Magnetic stirrer.
8. test system according to claim 7, it is characterised in that：The gas cylinder uses methane gas cylinder.
9. the special low-field nuclear magnetic resonance Multi probe quantitative test of hydrate based on any one of the claim 1-8 test systems
Method, it is characterised in that comprise the following steps：
(1) parallel soil sample is prepared：
Three parallel soil samples, i.e. test sample are prepared using identical process, three soil samples are of the same size, identical matter
Amount and identical porosity；
(2) it is not added with confined pressure normal temperature and pressure probe measurement：Without hydrate soil sample pore Structure Analysis；
Take a soil sample to be positioned over to be not added with confined pressure normal temperature and pressure probe, low field nuclear-magnetism is installed in after distillation saturation soil sample
On resonance analytical instrument, low-field nuclear magnetic resonance analyzer is run, obtains its T2 distribution curve, analysis is free of gas hydrates soil sample
Porosity distribution and do not demarcate porosity；
(3) it is not added with confined pressure cryogenic high pressure probe measurement：Quantitatively calibrating, determine transverse relaxation rate；
Take a soil sample to be positioned over again to be not added with confined pressure cryogenic high pressure probe, and connect itself and temperature confined pressure control module and hole
The annexation of clearance flow body injection module, the synthesizing methane hydrate in soil sample, calculated using gas flow conservation method during this
Hydrate concentration；At the same time the T2 distribution curves containing hydrate sediment that low-field nuclear magnetic resonance analyzer obtains are run,
Analyze the active porosity distribution characteristics of the soil sample containing gas hydrates and do not demarcate effecive porosity；
Synthesizing methane in the porosity calculation step is not demarcated without gas hydrates soil sample according to what is obtained in step (2)
The hydrate concentration of hydrate, and combine the above-mentioned hydrate calculated using gas flow conservation method and satisfy, it is determined that containing used in experiment
The transverse relaxation rate of hydrate sediment；
(4) confined pressure cryogenic high pressure probe measurement is added：The behavior of qualitative analysis pore scale containing hydrate sediment；
Take remaining soil sample to be positioned over to add in confined pressure cryogenic high pressure probe, and connect itself and temperature confined pressure control module and hole
The annexation of fluid injection module, according to the effective confining pressure of setting, method is prepared in soil sample using saturation methane distillation water circulation
Middle synthesizing methane hydrate, hydrate is gradually then decomposed by controlling gas saturation water to prepare container inner pressure, runs low field
Magnetic nuclear resonance analyzer obtains in lanthanum chloride hydrate and decomposable process the T2 distribution curves of test sample at different moments, with reference to step
(3) the transverse relaxation rate determined in, quantitative analysis lanthanum chloride hydrate and pore radius containing hydrate sediment point in decomposable process
The Evolution of cloth curve.
10. method of testing according to claim 9, it is characterised in that：In the step (4), can also have by changing
Imitate confined pressure, affecting laws of the quantitative analysis effective confining pressure to the distribution curve of pore radius containing hydrate sediment.
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