CN104390902A - Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate - Google Patents

Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate Download PDF

Info

Publication number
CN104390902A
CN104390902A CN201410668860.2A CN201410668860A CN104390902A CN 104390902 A CN104390902 A CN 104390902A CN 201410668860 A CN201410668860 A CN 201410668860A CN 104390902 A CN104390902 A CN 104390902A
Authority
CN
China
Prior art keywords
sediment
gas hydrate
hydrate
gas
distribution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410668860.2A
Other languages
Chinese (zh)
Other versions
CN104390902B (en
Inventor
宋永臣
杨明军
经文
刘卫国
赵越超
蒋兰兰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201410668860.2A priority Critical patent/CN104390902B/en
Publication of CN104390902A publication Critical patent/CN104390902A/en
Application granted granted Critical
Publication of CN104390902B publication Critical patent/CN104390902B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Geophysics And Detection Of Objects (AREA)

Abstract

The invention belongs to the field of geological exploration and resource development of gas hydrates and relates to a method for analyzing the pore distribution of sediment by virtue of the saturation change of a gas hydrate. According to the method, the gas hydrate is generated in the sediment by virtue of pressurization temperature reduction. In the decomposition process of the generated gas hydrate, the temperature remains unchanged. In a mode of gradually reducing the pressure, the hydrate is promoted to be gradually decomposed. The signal strength of water in the sediment in each decomposition stage and the pore distribution situation of the decomposed hydrate are measured by virtue of nuclear magnetic resonance imaging equipment. The size and total quantity of pores occupied by the gas hydrate decomposed in each stage are determined by virtue of the temperature and pressure of each decomposition stage, so that the pore distribution characteristics of the sediment are calculated and described by virtue of an image shot by nuclear magnetic resonance imaging. The method has the advantage that under the condition that the natural core structure is not destroyed, the internal porosity distribution characteristics of the sediment can be clearly identified by virtue of the generation decomposition process of the hydrate. The method is easy to operate.

Description

A kind of method utilizing gas hydrate saturation degree mutation analysis sediment distribution of pores
Technical field
The invention belongs to gas hydrate geologic prospecting and development of resources field, be specifically related to a kind of method utilizing gas hydrate saturation degree mutation analysis sediment distribution of pores.
Background technology
Along with the exhaustion day by day of conventional fossil fuel resource, the discovery of gas hydrate is undoubtedly the quantum jump of energy field.Occurring in nature gas hydrate are mainly distributed in the permafrost of abyssal sediment or land-based area, bring great difficulty to exploitation and utilization.The reliable geologic data data that can obtain accurately is portrayed to microphysics character such as sedimental domain size distribution, sedimentary structure and pore textures, for natural gas hydrate exploration exploitation provides significant data to support.
The sedimental method of analysis conventional at present has the methods such as intrusive mercury curve, X-ray diffraction, thin section identification, scanning electron microscope, although these can more clearly identify sedimental pore structure characteristic.But because occurring in nature natural gas hydrate deposits thing is mostly dispersed, in classic method test process, usually can destroy natural sediment structure, impact test accuracy.Due to hydrate balancing each other a little and there is corresponding relation between sediment factor of porosity under specified temp pressure, so utilize gas hydrate saturation degree to change, when not changing sediment formalness and inner structure, the distribution of research sediment factor of porosity is a kind of convenient and effective method.
From gas hydrate forming process, hydrate substitutes the water in sediment hole, and form hydrate deposit, hydrate may suspend in a fluid in hole, also may contact or cementing sedimentary particle.These microcosmic occurrence status and saturation degree change have relation closely with rock core particle diameter and arrayed feature thereof, to physical parameters such as sedimental pore texture, permeabilities, there is crucial effect, have also been changed earthquake wave propagation simultaneously, thus to the geophysical survey of hydrate and resource evaluation, there is material impact.
Summary of the invention
The invention provides a kind of method utilizing gas hydrate saturation degree mutation analysis sediment distribution of pores, be convenient to the exploration of natural gas hydrate resources, exploitation.
The present invention, by pressurization cooling, makes gas hydrate generate in sediment.In decomposable process after gas hydrate generates, keep temperature-resistant, adopt and progressively reduce pressure mode, hydrate is impelled progressively to decompose, and utilize Magnetic resonance imaging (MRI) equipment to measure the signal intensity of water in each catabolic phase sediment and the distribution of pores situation of decomposition water compound, in conjunction with the temperature and pressure of each catabolic phase, determine the pore size that the gas hydrate of each stage decomposition occupies and hole total amount, thus the image of syncaryon magnetic resonance imaging shooting calculates and depicts sedimental porosity distribution.
Technical scheme of the present invention is:
A kind of method utilizing gas hydrate saturation degree mutation analysis sediment distribution of pores, the core chamber that sediment to be analyzed puts into vacuum pressed saturation device is vacuumized, in core chamber, add deionized water soak sediment, certain external pressure is applied to core chamber, external pressure is determined according to sedimental loose and compactness extent, and this pressure makes sediment fully can absorb deionized water; Being taken out by water saturated for suction sediment is placed in basket, source of the gas, thermostatic bath, data acquisition monitoring system are all connected with Magnetic resonance imaging, sedimental basket will be housed and be placed in Magnetic resonance imaging, pass into the gas such as methane or carbon dioxide, open thermostatic bath, temperature in basket is reduced, according to the temperature of gas with various setting thermostatic bath, makes gas generate gas hydrate completely; After gas hydrate generates completely in sediment hole, what keep in basket is temperature-resistant, progressively step-down, and a part of gas hydrate decomposes; Continue step-down until gas hydrate decomposes completely, each step-down 0.2MPa, fell every ten minutes and once presses; According to the phase balance condition of gas hydrate under different aperture radius, the sediment pore-size that gas hydrate at corresponding decomposition pressure and temperature occupies instead can be released.
According to the signal intensity of water in each catabolic phase sediment of Magnetic resonance imaging record, the intensity value of each catabolic phase residual water compound can be obtained through process and conversion, thus the number percent of the void content of decomposition gas hydrate can be calculated, the image of Magnetic resonance imaging shooting records sedimental distribution of pores position simultaneously.
Obtain sedimental distribution of pores frequency histogram according to the sediment pore size of each catabolic phase and void content, distribution of pores frequency histogram is combined with distribution of pores location drawing picture, can intuitively finds out sedimental porosity distribution.
The present invention is not when destroying sediment structure, utilize the generation decomposable process of gas hydrate, clearly can identify sediment wood interior porosity distribution characteristics, and quantitative description has been carried out to it, compensate for directly inadequate by Magnetic resonance imaging gaging hole porosity distribution resolution shortcoming.This method is equally applicable to the test of nature natural gas hydrate deposit distribution of pores.Sedimental pore texture reflects the microphysics character of rock, because its structure is very complicated, how to characterize pore texture distribution characteristics most important to its seepage flow mechanism of understanding, method provided by the invention, simple to operate, effectively convenient, can effectively address this problem in laboratory conditions, simultaneously also for the exploration of gas hydrate and exploitation provide technical know-how support.
Accompanying drawing explanation
Fig. 1 is each catabolic phase distribution of pores location drawing.
Fig. 2 is porosity distribution figure.
Fig. 3 is distribution of pores frequency histogram.
Embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme.
Embodiment
By pressurize in vacuum pressed saturation device saturated after sediment be placed in basket, basket to be put in Magnetic resonance imaging and to connect the pipeline of source of the gas, thermostatic bath, data acquisition monitoring system, open valve, utilize gas injection pump in basket, inject valve-off after methane gas to 3.3MPa.Leave standstill three to four hours, methane is fully dissolved in water.After pressure stabilisationly open thermostatic bath again, make temperature in basket drop to 274.15K.The pressure and temperature data in Real-time Collection core holding unit understood by pressure transducer and thermopair, can be observed the situation of change of pressure and temperature by data acquisition monitoring system, Magnetic resonance imaging also can the change in signal strength of water and sediment distribution of pores situation in real time record sediment hole.When pressure declines suddenly, show have methane hydrate to generate in a large number, at this moment continue to keep design temperature, treat that methane hydrate generates completely.
After methane hydrate generates completely, just can carry out progressively step-down and decompose.Maintain the temperature at 274.15K constant, progressively step-down, part methane hydrate can first decompose, generally that hydrate in fine porosity first decomposes, decompose after hydrate in macropore, continue step-down until methane hydrate decomposes completely, each Amplitude of Hypotensive is 0.2MPa, falls once press every ten minutes.Along with the decomposition of hydrate, Magnetic resonance imaging can record the aperture position image that methane hydrate decomposes, and as shown in Figure 1, black represents solid, and grey represents the water after methane hydrate decomposition.
In the 0min moment, start the state before step-down after image representative methane hydrate generates completely, start step-down subsequently, the image in 10min moment be first time step-down decompose after image, be exactly the position of decomposition of hydrate by the black position becoming ash.Like this, under temperature constant state, reduce a pressure every ten minutes, until methane hydrate decomposes completely, just can obtain the image that a series of methane hydrate decomposes position, i.e. different size aperture position distribution plan.In order to find out the position of various sizes distribution of pores more clearly, the image of adjacent twice step-down can be done subtraction, after obtaining step-down each time, having the aperture position that methane hydrate decomposes, as shown in Figure 2.
According to the phase balance condition of methane hydrate under different aperture radius, the sediment pore-size that methane hydrate at corresponding decomposition pressure and temperature occupies instead can be released.Magnetic resonance imaging can record the signal intensity of water in each catabolic phase sediment, can be calculated the intensity value of each catabolic phase residual water compound through formula (1).
S h = 1.25 × ( I 0 - I i ) × S w 0 I 0 × 100 % - - - ( 1 )
Note: S in formula w0for initial water saturation degree, be 1 in this experiment; I 0and I irepresent initial time and the MI value in i moment respectively.
Shared by the methane hydrate of each catabolic phase pressure that experiment obtains, corresponding pore-size and every stage decomposition, void content number percent is as shown in table 1.Pore-size at the corresponding pressure found according to each catabolic phase and temperature, can make sedimental distribution of pores frequency histogram in conjunction with the void content obtained by saturation degree, as shown in Figure 3.
The characteristic quantity of each catabolic phase of table 1
Time (min) 0 10 20 30
Pressure (MPa) 3.3 3.1 2.9 2.7
Pore-size (nm) 60 200 300
Remaining hydrate concentration 0.3123 0.2783 0.0122 0
Void content 10.89% 85.21% 3.90%
Fig. 3 and Fig. 2 is combined, can intuitively find out sedimental porosity distribution.As can be seen from distribution of pores frequency histogram, the hole of 200nm side-to-side dimensions is maximum, and the void content of all the other two sizes is less, illustrates that the sedimental distribution of pores of this experiment is more even.

Claims (2)

1. utilize a method for gas hydrate saturation degree mutation analysis sediment distribution of pores, it is characterized in that,
(1) core chamber sediment to be analyzed being put into vacuum pressed saturation device vacuumizes, in core chamber, add deionized water soak sediment, apply external pressure according to sedimental loose and compactness extent to core chamber, external pressure makes sediment fully absorb deionized water;
(2) water saturated for suction sediment taking-up is placed in basket, source of the gas, thermostatic bath, data acquisition monitoring system are all connected with Magnetic resonance imaging, sedimental basket will be housed and be placed in Magnetic resonance imaging, pass into gas, open thermostatic bath, temperature in basket is reduced, according to the temperature of gas with various setting thermostatic bath, makes gas generate gas hydrate completely;
(3) after gas hydrate generates completely in sediment hole, what keep in basket is temperature-resistant, progressively step-down, and a part of gas hydrate decomposes, and continues step-down until gas hydrate decomposes completely; Each step-down 0.2MPa, fell every ten minutes and once presses;
(4) by the phase balance condition of gas hydrate under different aperture radius, the anti-sediment pore-size released gas hydrate at corresponding decomposition pressure and temperature and occupy;
(5) signal intensity of water in each catabolic phase sediment of Magnetic resonance imaging record, the intensity value of each catabolic phase residual water compound is obtained through process, calculate the number percent of the void content of decomposition gas hydrate, the image of Magnetic resonance imaging shooting records sedimental distribution of pores position simultaneously;
(6) according to sediment pore size and the void content of each catabolic phase, obtain sedimental distribution of pores frequency histogram, distribution of pores frequency histogram is combined with distribution of pores location drawing picture, the sedimental porosity distribution of observation directly perceived.
2. method according to claim 1, is characterized in that, described gas is methane or carbon dioxide.
CN201410668860.2A 2014-11-20 2014-11-20 Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate Active CN104390902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410668860.2A CN104390902B (en) 2014-11-20 2014-11-20 Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410668860.2A CN104390902B (en) 2014-11-20 2014-11-20 Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate

Publications (2)

Publication Number Publication Date
CN104390902A true CN104390902A (en) 2015-03-04
CN104390902B CN104390902B (en) 2017-01-25

Family

ID=52608832

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410668860.2A Active CN104390902B (en) 2014-11-20 2014-11-20 Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate

Country Status (1)

Country Link
CN (1) CN104390902B (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106526079A (en) * 2016-10-27 2017-03-22 中国石油大学(北京) Method used for studying tight sandstone pore-throat structure dynamic change
CN106932832A (en) * 2015-12-30 2017-07-07 核工业北京地质研究院 One kind contains CO2Fluid inclusion light microscope recognition methods
CN107238521A (en) * 2017-06-07 2017-10-10 中国石油大学(华东) A kind of preparation method of tundra hydrate rock core
CN108519399A (en) * 2018-04-24 2018-09-11 中国地质大学(北京) Fluid phase change generating means between a kind of combination nuclear magnetic resonance technique research hole
CN109374489A (en) * 2018-08-21 2019-02-22 中国地质大学(武汉) The hydrate sediment NMR relaxation signals amount caliberating device and method of joint X-CT technology
CN109441429A (en) * 2018-12-27 2019-03-08 广州海洋地质调查局 A kind of solid time-lapse seismic observation reservoir performance monitor method and system
CN110174335A (en) * 2019-03-12 2019-08-27 北京建筑大学 The equivalent maximum diameter of hole of fibrous material based on measurement obtains system and method
CN112485281A (en) * 2020-10-19 2021-03-12 中国地质大学(北京) Method for dynamically measuring gas hydrate saturation and permeability in porous medium
CN112540098A (en) * 2020-12-02 2021-03-23 中国地质大学(北京) Device and method for measuring phase equilibrium condition of gas hydrate in sediment
CN112800699A (en) * 2021-02-17 2021-05-14 大连理工大学 Early warning method for simulating hydrate blockage of submarine gas pipeline transportation
CN112800626A (en) * 2021-02-17 2021-05-14 大连理工大学 Early warning method for simulating circulation submarine pipeline hydrate blockage
CN113007606A (en) * 2021-02-17 2021-06-22 大连理工大学 Flowing safety early warning method for seabed gas transmission pipeline with falling hydrate deposition structure
WO2021129315A1 (en) * 2019-12-26 2021-07-01 中国科学院广州能源研究所 Method for calculating pore distribution of marine sediment layer
CN117054460A (en) * 2023-10-12 2023-11-14 中国科学院地质与地球物理研究所 Method for calculating saturation of different fluids based on refrigeration electron microscope

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246117A (en) * 2008-03-25 2008-08-20 中国科学院力学研究所 Gas-hydrate synthesizing and macro-microscopic mechanics nature synthetic experiment system
CN101458218A (en) * 2008-12-28 2009-06-17 大连理工大学 Carbon dioxide oil-displacing nmr imaging detection device
CN102062742A (en) * 2010-12-15 2011-05-18 大连理工大学 Sand-filling type clamp fastener for nuclear magnetic resonance imaging
CN102495090A (en) * 2011-11-24 2012-06-13 大连理工大学 Device and method for low-temperature high-pressure nuclear magnetic resonance imaging of natural gas hydrate
CN102901987A (en) * 2011-07-29 2013-01-30 中国海洋石油总公司 Core barrel for nuclear magnetic resonance imager

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246117A (en) * 2008-03-25 2008-08-20 中国科学院力学研究所 Gas-hydrate synthesizing and macro-microscopic mechanics nature synthetic experiment system
CN101458218A (en) * 2008-12-28 2009-06-17 大连理工大学 Carbon dioxide oil-displacing nmr imaging detection device
CN102062742A (en) * 2010-12-15 2011-05-18 大连理工大学 Sand-filling type clamp fastener for nuclear magnetic resonance imaging
CN102901987A (en) * 2011-07-29 2013-01-30 中国海洋石油总公司 Core barrel for nuclear magnetic resonance imager
CN102495090A (en) * 2011-11-24 2012-06-13 大连理工大学 Device and method for low-temperature high-pressure nuclear magnetic resonance imaging of natural gas hydrate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
刘瑜 等: "多孔介质断面可视化与孔隙度测量的MRI方法", 《测试技术学报》 *
姚蕾 等: "天然气水合物实验检测与分析技术", 《能源与环境》 *
杨明军: "原位条件下水合物形成与分解研究", 《中国博士学位论文全文数据库 基础科学辑》 *
魏厚振 等: "含天然气水合物沉积物相平衡问题研究综述", 《岩土力学》 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106932832A (en) * 2015-12-30 2017-07-07 核工业北京地质研究院 One kind contains CO2Fluid inclusion light microscope recognition methods
CN106526079A (en) * 2016-10-27 2017-03-22 中国石油大学(北京) Method used for studying tight sandstone pore-throat structure dynamic change
CN107238521B (en) * 2017-06-07 2019-09-10 中国石油大学(华东) A kind of production method of tundra hydrate rock core
CN107238521A (en) * 2017-06-07 2017-10-10 中国石油大学(华东) A kind of preparation method of tundra hydrate rock core
CN108519399A (en) * 2018-04-24 2018-09-11 中国地质大学(北京) Fluid phase change generating means between a kind of combination nuclear magnetic resonance technique research hole
CN109374489B (en) * 2018-08-21 2020-07-07 中国地质大学(武汉) Hydrate deposit NMR relaxation signal quantity calibration device and method combining X-CT technology
CN109374489A (en) * 2018-08-21 2019-02-22 中国地质大学(武汉) The hydrate sediment NMR relaxation signals amount caliberating device and method of joint X-CT technology
CN109441429A (en) * 2018-12-27 2019-03-08 广州海洋地质调查局 A kind of solid time-lapse seismic observation reservoir performance monitor method and system
CN110174335A (en) * 2019-03-12 2019-08-27 北京建筑大学 The equivalent maximum diameter of hole of fibrous material based on measurement obtains system and method
CN110174335B (en) * 2019-03-12 2022-03-25 北京建筑大学 Fiber material equivalent maximum aperture obtaining system and method based on measurement
WO2021129315A1 (en) * 2019-12-26 2021-07-01 中国科学院广州能源研究所 Method for calculating pore distribution of marine sediment layer
CN112485281A (en) * 2020-10-19 2021-03-12 中国地质大学(北京) Method for dynamically measuring gas hydrate saturation and permeability in porous medium
CN112540098A (en) * 2020-12-02 2021-03-23 中国地质大学(北京) Device and method for measuring phase equilibrium condition of gas hydrate in sediment
CN112800626A (en) * 2021-02-17 2021-05-14 大连理工大学 Early warning method for simulating circulation submarine pipeline hydrate blockage
CN113007606A (en) * 2021-02-17 2021-06-22 大连理工大学 Flowing safety early warning method for seabed gas transmission pipeline with falling hydrate deposition structure
CN112800699A (en) * 2021-02-17 2021-05-14 大连理工大学 Early warning method for simulating hydrate blockage of submarine gas pipeline transportation
CN113007606B (en) * 2021-02-17 2022-04-01 大连理工大学 Flowing safety early warning method for seabed gas transmission pipeline with falling hydrate deposition structure
CN117054460A (en) * 2023-10-12 2023-11-14 中国科学院地质与地球物理研究所 Method for calculating saturation of different fluids based on refrigeration electron microscope
CN117054460B (en) * 2023-10-12 2023-12-08 中国科学院地质与地球物理研究所 Method for calculating saturation of different fluids based on refrigeration electron microscope

Also Published As

Publication number Publication date
CN104390902B (en) 2017-01-25

Similar Documents

Publication Publication Date Title
CN104390902B (en) Method for analyzing pore distribution of sediment by virtue of saturation change of gas hydrate
Tan et al. Experimental study of permeability and its anisotropy for shale fracture supported with proppant
Ju et al. Laboratory in situ CT observation of the evolution of 3D fracture networks in coal subjected to confining pressures and axial compressive loads: a novel approach
Wang et al. Physical simulation of temperature influence on methane sorption and kinetics in coal: Benefits of temperature under 273.15 K
CN107894386B (en) Supercritical carbon dioxide injects the quantitative evaluation method influenced on low permeability sandstone reservoir pore throat character
US11098565B2 (en) Method for estimating permeability of fractured rock formations from induced slow fluid pressure waves
Sun et al. Experimental study on pore structure evolution of coal in macroscopic, mesoscopic, and microscopic scales during liquid nitrogen cyclic cold-shock fracturing
WO2017024530A1 (en) Method for calculating content of organic carbon in hydrocarbon source rock
Tang et al. Temperature-dependent diffusion process of methane through dry crushed coal
CA2903451C (en) Determining continuous capillary pressure curves for subsurface earth formations using saturation and nmr log data
Wu et al. Characterization of pore structure of tight sandstone reservoirs based on fractal analysis of NMR echo data
Achang et al. The influence of particle size, microfractures, and pressure decay on measuring the permeability of crushed shale samples
CN104655826B (en) A kind of method and device of the absorption parameter detecting compact reservoir ADSORPTION STATE crude oil
Hu et al. A method to determine nuclear magnetic resonance T2 cutoff value of tight sandstone reservoir based on multifractal analysis
Rafatian et al. Petrophysical characterization of the pore space in permian wolfcamp rocks
Zhang et al. In-situ observation for natural gas hydrate in porous medium: Water performance and formation characteristic
CN106525681A (en) Method for determining pore diameter of shale reservoir
CN106644879B (en) A kind of method and device of determining rock core different aperture component permeability contribution margin
Xin et al. An improved method to determine accurate porosity of low-rank coals by nuclear magnetic resonance
Niu et al. Real-time and in-situ assessment of conduit permeability through diverse long-period tremors beneath Aso volcano, Japan
CN116738136B (en) Calculation method for seabed methane gas release under action of internal solitary wave
Liu* et al. Determining the permeability of hydrate-bearing slity-fine sands with water transient flow
CN112147053B (en) Microbial carbonate reservoir buried pyrolysis pore-increasing quantitative evaluation method and device
CN111426617B (en) Quantitative prediction method for porosity of dense reservoir of land lake basin under geological conditions
CN110306977A (en) Nuclear magnetic resonance T2Compose hydrocarbonaceous bearing calibration and system

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant