阅读说明：本技术 一种模拟致密岩石微纳孔隙环境的油气赋存相态测定方法 (A kind of Oil And Gas Occurrence phase measuring method for simulating tight rock micro-nano hole environment ) 是由 盛茂 田守嶒 王天宇 李根生 黄中伟 徐泉 宋先知 王海柱 于 2019-08-15 设计创作，主要内容包括：本发明公开了一种模拟致密岩石微纳孔隙环境的油气赋存相态测定方法,包括如下步骤：步骤一,对阵列纳米管的管壁进行分子修饰,得到致密岩石微纳孔隙模型；步骤二,将步骤一得到的致密岩石微纳孔隙模型置于容器中,向容器中充注储层油气,并对容器加压加热；步骤三,对容器进行同步辐射、中子散射和核磁共振测试,得到储层油气在致密岩石微纳孔隙模型中的原子排布和密度；步骤四,分析步骤三得到的原子排布和密度,表征模拟致密岩石微纳孔隙环境的油气赋存相态。本发明采用阵列纳米管模仿致密岩石微纳尺度孔隙,通过对列阵纳米管管壁的分子修饰,使其具有与致密岩石类似的原子种类和元素组成,从而实现真实描述致密岩石微纳尺度孔隙结构。(The invention discloses a kind of Oil And Gas Occurrence phase measuring methods for simulating tight rock micro-nano hole environment, include the following steps: step 1, carry out molecular modification to the tube wall of arrayed nanotube, obtain tight rock micro-nano pore model；The tight rock micro-nano pore model that step 1 obtains is placed in container, reservoir hydrocarbons is filled into container, and to container pressurized, heated by step 2；Step 3 synchronizes radiation, neutron scattering and nuclear magnetic resonance to container and tests, obtains Atomic Arrangement and density of the reservoir hydrocarbons in tight rock micro-nano pore model；Step 4, the Atomic Arrangement and density that analytical procedure three obtains, the Oil And Gas Occurrence phase of characterization simulation tight rock micro-nano hole environment.The present invention imitates tight rock micro/nano-scale hole using arrayed nanotube, by the molecular modification to array nanometer tube wall, the atomic species and element composition similar with tight rock is made it have, to realize true description tight rock micro/nano-scale pore structure.)

1. a kind of Oil And Gas Occurrence phase measuring method for simulating tight rock micro-nano hole environment, which is characterized in that including as follows Step:

Step 1 carries out molecular modification to the tube wall of arrayed nanotube, obtains tight rock micro-nano pore model；

The tight rock micro-nano pore model that step 1 obtains is placed in container, reservoir hydrocarbons is filled into container by step 2, And to container pressurized, heated；

Step 3 synchronizes radiation, neutron scattering and nuclear magnetic resonance to container and tests, it is micro- in tight rock to obtain reservoir hydrocarbons The Atomic Arrangement and density received in pore model；

Step 4, the Atomic Arrangement and density that analytical procedure three obtains, the oil gas of characterization simulation tight rock micro-nano hole environment Chemical fraction.

2. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 1, special Sign is, in step 1, the arrayed nanotube by silicon wafer oriented growth obtain.

3. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 2, special Sign is, further includes the steps that being processed by shot blasting silicon wafer before oriented growth arrayed nanotube on silicon wafer.

4. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 3, special Sign is, described to be processed by shot blasting to silicon wafer to use argon ion polished silicon slice.

5. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 1, special Sign is, in step 1, it includes: analysis tight rock that the tube wall to arrayed nanotube, which carries out the detailed process of molecular modification, Element composition, molecular modification is carried out according to tube wall of the obtained element composition ratio of analysis to arrayed nanotube.

6. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 5, special Sign is that the element group of the analysis tight rock becomes red by X-ray diffraction, x-ray photoelectron spectroscopy and fourier conversion Outside line spectrum analysis obtains the element composition of tight rock.

7. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 5 or 6, It is characterized in that, the element composition of the tight rock includes carbon, oxygen, nitrogen, p and s.

8. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 1, special Sign is, in step 2, the reservoir hydrocarbons are one of methane, ethane and carbon dioxide or a variety of.

9. the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment according to claim 1, special Sign is, in step 2, described is specially the ground of reservoir where being forced into tight rock to container to container heating pressurization Stressor layer and formation temperature.

10. a kind of application of neutron scattering methods methane Chemical fraction in characterization tight rock micro/nano-scale hole.

Technical field

The present invention relates to oil and gas production technique fields.More particularly, to a kind of simulation tight rock micro-nano The Oil And Gas Occurrence phase measuring method of hole environment.

Background technique

China's unconventional oil and gas (refering in particular to shale oil, shale gas, fine and close rock gas etc.) is resourceful, wherein land unconventional day Right 132 tcm (according to the 4th oil and gas resource evaluation result of China Petroleum) of gas geological resources, is conventional gas money 3 times of source amount, it has also become the important foundation of oil gas sustainable development.However unconventional oil and gas exploitation difficulty is very big, Oil And Gas Occurrence In the extremely low tight rock micro-nano hole crazing seam of permeability.Oil And Gas Occurrence phase is the basis of oil gas high-efficiency mining.

Physics research shows that fluid, will be with " class solid-state is close in high temperature and pressure and confinement space (such as nano pore) Heap " form exists, and density is far more than free state gas density.Tight rock develops a large amount of micro-nano ducts, buried in underground High temperature and high pressure environment, supporting environment is still unclear, while natural gas Chemical fraction predicts Adsorption Natural Gas amount, gas output And reserve estimate is of great significance.

Therefore, the present invention provides a kind of Oil And Gas Occurrence phase measuring method for simulating tight rock micro-nano hole environment, with It solves the above problems.

Summary of the invention

It is an object of the present invention to provide a kind of Oil And Gas Occurrence phase surveys for simulating tight rock micro-nano hole environment Determine method.Chemical fraction of the methane in tight rock micro/nano-scale hole under the conditions of the true stratum of this method accurate description, It, to the high-penetration ability of substance, provides crucial means using neutron for methane molecule arrangement mode in detection autoclave； Nanotube array is produced on silicon wafer simultaneously and provides quick, accurate approach for accurate simulation tight rock micro-nano hole.

It is another object of the present invention to provide a kind of neutron scattering methods in tight rock micro/nano-scale hole methane Application in Chemical fraction characterization.

In order to achieve the above objectives, the present invention adopts the following technical solutions:

A kind of Oil And Gas Occurrence phase measuring method for simulating tight rock micro-nano hole environment, includes the following steps:

Step 1 carries out molecular modification to the tube wall of arrayed nanotube, obtains tight rock micro-nano pore model；

The tight rock micro-nano pore model that step 1 obtains is placed in container, reservoir is filled into container by step 2 Oil gas, and to container pressurized, heated；

Step 3 synchronizes radiation, neutron scattering and nuclear magnetic resonance to container and tests, obtains reservoir hydrocarbons in fine and close rock Atomic Arrangement and density in stone micro-nano pore model；

Step 4, the Atomic Arrangement and density that analytical procedure three obtains, characterization simulation tight rock micro-nano hole environment Oil And Gas Occurrence phase.

Preferably, in step 1, the arrayed nanotube by silicon wafer oriented growth obtain；Further, in silicon Further include the steps that being processed by shot blasting silicon wafer before on piece oriented growth arrayed nanotube；Further, using argon ion Polished silicon slice.

Preferably, in step 1, the detailed process that the tube wall to arrayed nanotube carries out molecular modification includes: analysis The element of tight rock forms, and the element composition ratio obtained according to analysis carries out molecular modification to the tube wall of arrayed nanotube.

Further, the element group of the analysis tight rock, which becomes, passes through X-ray diffraction (XRD), x-ray photoelectron energy Spectrum (XPS) and fourier conversion infrared spectrum (FTIR) analysis obtain the element composition of tight rock.

Preferably, the element composition of the tight rock includes carbon, oxygen, nitrogen, p and s.

Preferably, in step 2, the reservoir hydrocarbons are one of methane, ethane and carbon dioxide or a variety of.

Preferably, in step 2, described is specially to be forced into where tight rock to container to container heating pressurization The strata pressure and formation temperature of reservoir.

Preferably, in step 2, the container is high temperature and high pressure kettle；Further, the material of the high temperature and high pressure kettle is stone English meets 120 DEG C of high temperature resistant and pressure resistance 100MPa, can be used for nuclear magnetic resonance test.

Preferably, in step 3, the analysis of Atomic Arrangement and density is to be analyzed using software, such as can be Mestrenova nuclear magnetic data processing software.

The present invention also provides a kind of neutron scattering methods characterization tight rock micro/nano-scale hole in methane preservation phase The application of state.

Tight rock hole is the main place of methane preservation and flowing, and constituent structure is complicated, it is difficult to accurate characterization first Alkane is in the Chemical fraction of tight rock micro/nano-scale hole, and the present invention is made by the molecular modification to array nanometer tube wall There is the atomic species similar with tight rock and element to form for it, to simulate the micro/nano-scale hole of tight rock complexity；

Technical principle basis of the invention is synchrotron radiation, neutron scattering and nuclear magnetic resonance technique；Wherein, synchrotron radiation is The electromagnetic radiation that the charged particle of speed close to the light velocity is released when arcuately track moves in magnetic field.Synchrotron radiation be have from Continuous spectrum, high intensity, highly collimated, high degree of polarization within the scope of far infrared to X-ray, characteristic such as accurately control at the excellent properties Light-pulse generator, many front line science technical research that can be cannot achieve to carry out other light sources；Neutron scattering technology benefit With the static structure of neutron scattering methods research substance and the micro kinetics property of substance.Neutron has not charged, penetration power By force, can identify isotope, it is sensitive to light element compared with X-ray, have many advantages, such as magnetic moment, therefore Neutron scattering technology is as a kind of Unique, the research structure of matter and dynamic characteristic from atom and molecular scale the characterization method；Nuclear magnetic resonance technique is wide It is general to be applied to the fields such as medical diagnosis, petroleum exploration and development, agricultural, video, reusable, non-destructive testing, inspection with sample Degree of testing the speed waits remarkable advantages fastly.The means that nuclear magnetic resonance technique is detected as a kind of rock physics analysis of experiments, by measuring rock The nuclear-magnetism characteristic of stone Fluid in Pore, density of the Lai Fanying oil gas in fine and close hole.Above-mentioned synchrotron radiation, neutron scattering and core Mr techniques are existing method, and the present invention repeats no more this.

The present invention characterizes the Chemical fraction that Neutron scattering technology is applied to tight rock micro/nano-scale hole reservoir hydrocarbons, The arrangement mode of reservoir hydrocarbons molecule in fine description micro-nano hole is reservoir hydrocarbons preservation under the conditions of the true stratum of accurate judgement Phase provides crucial laboratory facilities；Nanotube simulates tight rock micro/nano-scale pore characteristic and provides original for characterization pore structure Manage foundation；Neutron scattering analyzes software and provides technical support for the differentiation of reservoir hydrocarbons Chemical fraction.

Beneficial effects of the present invention are as follows:

(1) present invention imitates tight rock micro/nano-scale hole using arrayed nanotube, by array nanometer tube wall Molecular modification, make it have the atomic species similar with tight rock and element composition, true describe fine and close rock to realize Stone micro/nano-scale pore structure；

(2) present invention uses high temperature confining pressure kettle, can truly provide stratum high-temperature hyperbaric environment, mentions for Oil And Gas Occurrence condition For material base；

(3) present invention combines synchrotron radiation, neutron scattering and magnetic nuclear resonance method, the preservation phase of Study In Reservoir oil gas State provides crucial laboratory facilities for the Chemical fraction of reservoir hydrocarbons under the conditions of the true stratum of accurate judgement.

Detailed description of the invention

Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.

Fig. 1 shows the stream of the Oil And Gas Occurrence phase measuring method of simulation tight rock micro-nano hole environment provided by the invention Cheng Tu.

Fig. 2 shows tight rock sample drawings in the embodiment of the present invention 1.

Fig. 3 shows the element composition figure of tight rock sample in the embodiment of the present invention 1.

Specific embodiment

In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.

Since tight rock develops a large amount of micro-nano ducts, at the same it is buried in underground high temperature and high pressure environment, supporting environment Still unclear, to solve the above problems, the present invention provides a kind of Oil And Gas Occurrence phases for simulating tight rock micro-nano hole environment State measuring method, process is as shown in Figure 1, include the following steps:

S101, molecular modification is carried out to the tube wall of arrayed nanotube, obtains tight rock micro-nano pore model；

S102, the tight rock micro-nano pore model that step S101 is obtained is placed in container, reservoir is filled into container Oil gas, and to container pressurized, heated；

S103, radiation, neutron scattering and nuclear magnetic resonance test are synchronized to container, obtain reservoir hydrocarbons in tight rock Atomic Arrangement and density in micro-nano pore model；

The Atomic Arrangement and density that S104, analytical procedure S103 are obtained, characterization simulation tight rock micro-nano hole environment Oil And Gas Occurrence phase.

The present invention imitates tight rock micro/nano-scale hole using arrayed nanotube；By the tube wall to arrayed nanotube into Row molecular modification makes it have tight rock pore surface property；True formation temperature is simulated by heating pressurization to container And pressure environment；Pass through atom site in nanotube of synchrotron radiation, neutron scattering and nuclear magnetic resonance research reservoir hydrocarbons, row Column mode and density, thus the Oil And Gas Occurrence phase of accurate Characterization tight rock micro-nano hole environment.Those skilled in the art answer When understanding, synchrotron radiation, neutron scattering and nuclear magnetic resonance test method are convenient technical process, and this will not be repeated here.

As one preferred embodiment of the invention, in S101, the preparation of the arrayed nanotube includes the following steps: Using argon ion polished silicon slice, oriented growth obtains arrayed nanotube on silicon wafer after a polish.Those skilled in the art should Understand, is conventional method in the method for silicon wafer growth arrayed nanotube, this will not be repeated here.

It is described that molecular modification is carried out to arrayed nanotube tube wall in S101 as one preferred embodiment of the invention Detailed process include: by X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and fourier convert infrared spectrum (FTIR) the element composition of tight rock is analyzed, the element composition ratio obtained according to analysis carries out the tube wall of arrayed nanotube Molecular modification；Further, the element composition of the tight rock includes carbon, oxygen, nitrogen, p and s etc..Those skilled in the art It should be understood that the method for carrying out molecular modification to the tube wall of arrayed nanotube is conventional method, this will not be repeated here.

As one preferred embodiment of the invention, in S101, the reservoir hydrocarbons are methane, ethane and carbon dioxide One of or it is a variety of.

To provide true stratum high temperature and high pressure environment, material base is provided for Oil And Gas Occurrence condition, as the present invention one Preferred embodiment, in S102, described is specially to be forced into where tight rock to store up to container to container heating pressurization The strata pressure and formation temperature of layer.

To guarantee that container is able to bear the strata pressure and formation temperature of reservoir, as a preferred embodiment party of the invention Formula, in S102, the container is high temperature and high pressure kettle；Further, the material of the high temperature and high pressure kettle is quartz, meets high temperature resistant 120 DEG C and pressure resistance 100MPa, it can be used for nuclear magnetic resonance test.

As one preferred embodiment of the invention, in S104, the analysis of Atomic Arrangement and density is using software point Analysis.

As another aspect of the present invention, the present invention also provides a kind of neutron scattering methods in characterization tight rock micro-nano The application of methane Chemical fraction in pore dimension.

In the following, being described further by embodiment to the contents of the present invention.