[go: up one dir, main page]

CN111238163B - Mixed working medium high-pressure gas liquefaction and supercooling system - Google Patents

Mixed working medium high-pressure gas liquefaction and supercooling system Download PDF

Info

Publication number
CN111238163B
CN111238163B CN202010090159.2A CN202010090159A CN111238163B CN 111238163 B CN111238163 B CN 111238163B CN 202010090159 A CN202010090159 A CN 202010090159A CN 111238163 B CN111238163 B CN 111238163B
Authority
CN
China
Prior art keywords
gas
mixed working
pressure
working medium
working fluid
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.)
Active
Application number
CN202010090159.2A
Other languages
Chinese (zh)
Other versions
CN111238163A (en
Inventor
公茂琼
王昊成
郭浩
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.)
Technical Institute of Physics and Chemistry of CAS
Original Assignee
Technical Institute of Physics and Chemistry of CAS
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 Technical Institute of Physics and Chemistry of CAS filed Critical Technical Institute of Physics and Chemistry of CAS
Priority to CN202010090159.2A priority Critical patent/CN111238163B/en
Publication of CN111238163A publication Critical patent/CN111238163A/en
Application granted granted Critical
Publication of CN111238163B publication Critical patent/CN111238163B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0015—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0017—Oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
    • F25J1/0219—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle in combination with an internal quasi-closed refrigeration loop, e.g. using a deep flash recycle loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0225—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using other external refrigeration means not provided before, e.g. heat driven absorption chillers
    • F25J1/0227—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using other external refrigeration means not provided before, e.g. heat driven absorption chillers within a refrigeration cascade
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0244—Operation; Control and regulation; Instrumentation
    • F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/906—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by heat driven absorption chillers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention provides a mixed working medium high-pressure gas liquefaction and supercooling system, which comprises: the mixed working medium throttling refrigeration system comprises a gas pressurization unit, a mixed working medium refrigerator unit and a supercooling unit, wherein the gas pressurization unit comprises a gas compressor and a rear cooler, the mixed working medium refrigerator unit comprises a mixed working medium main refrigeration cycle, and the supercooling unit comprises a supercooling heat exchanger, a throttling element and a liquid storage tank.

Description

Mixed working medium high-pressure gas liquefaction and supercooling system
Technical Field
The invention relates to the technical field of mixed working medium refrigeration precooling, in particular to a mixed working medium high-pressure gas liquefaction and supercooling system.
Background
Liquefied gases are important industrial products. The greater the supercooling degree of the liquefied gas, the smaller the storage and transportation difficulty of the liquefied gas, and the smaller the flash evaporation loss in the use process. In the case of nitrogen and oxygen liquefaction, the development of a conventional large-scale air separation plant is mature and is also a main source of liquefied gas in the market, but the product mainly comprises gas nitrogen and gas oxygen, and the liquid nitrogen and liquid oxygen gas are only byproducts accounting for a very small part of the yield. The preparation of the extremely large-scale liquefied gas requires a special liquefaction process to pressurize the gas nitrogen to high pressure and then liquefy the gas nitrogen again, and the higher the liquefaction pressure is, the lower the unit liquefaction energy consumption is. The current methods for realizing larger refrigerating capacity are gas expansion refrigeration cycle and mixed working medium throttling refrigeration cycle based on dividing wall type heat return. And with the gas expansion refrigeration cycle, the mixed working medium throttling refrigeration cycle has obviously higher efficiency and smaller compressor discharge capacity in the aspect of gas cooling liquefaction, does not contain low-temperature moving parts, and is an ideal cold energy source for gas liquefaction.
However, for the liquefied gas to be liquefied with a high normal pressure boiling point such as natural gas and the like (about (-161 ℃) and above), because the liquid phase sensible heat release plays a leading role, the temperature-load characteristic of the supercooling end of the liquefied gas is linear, the matching effect with the mixed working medium is poor, and the efficiency is low, so that an additional flow structure needs to be arranged to optimize the matching of the supercooling section. For the liquefied gas to be liquefied with lower normal pressure boiling point, such as nitrogen gas (196 ℃ below zero) and the like, except for the problem of load matching of a supercooling section, the refrigeration temperature required by a supercooling stage is lower and is usually lower than-180 ℃, and the mixed working medium throttling refrigerating machine has serious performance attenuation in a temperature region below-180 ℃, so that the liquefied gas is difficult to be directly supercooled to be lower, and therefore other flow structures are also required to be added to make up for the performance short plate of the mixed working medium throttling refrigerating machine at the lower refrigeration temperature.
Disclosure of Invention
Therefore, there is a need to provide a mixed working medium high-pressure gas liquefaction and supercooling system with a simple structure, which can realize high-efficiency refrigeration, aiming at the defects existing in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a mixed working medium high-pressure gas liquefying and supercooling system, which comprises: the mixed working medium refrigerating system comprises a mixed working medium main cold circulation, and the supercooling unit comprises a distributor, a supercooling heat exchanger, a main throttling element, a liquefied gas throttling element and a liquid storage tank, wherein:
the low-pressure feed gas enters the after-cooler for cooling after being pressurized by the gas compressor, and the formed high-pressure feed gas enters the pre-cooling heat exchanger;
the low-pressure feed gas enters the after-cooler for cooling after being pressurized by the gas compressor, and the formed high-pressure feed gas enters the mixed working medium refrigerating machine unit;
the mixed working medium refrigerating machine unit comprises a mixed working medium main cooling circulation and is used for providing refrigerating capacity for gas liquefaction; the mixed working medium main cooling cycle can adopt various configurations such as one-time throttling cycle, separation cycle and the like;
the high-pressure feed gas which is cooled to a low temperature and liquefied in the mixed working medium refrigerating unit is divided into two parts by the distributor, one part of the high-pressure liquefied feed gas enters the supercooling heat exchanger and is supercooled to-150 ℃ to-190 ℃ by the low-pressure steam, and the supercooled liquefied gas is throttled by the liquefied gas throttling element and enters the liquid storage tank to obtain supercooled liquid; and the other part of the high-pressure liquefied raw material gas is throttled to be close to the normal pressure by the main throttling element, cooled to the temperature of-152 ℃ to-192 ℃ below zero, enters the supercooling heat exchanger to provide cold energy, is gasified to form low-pressure steam, is reheated by the mixed working medium refrigerating unit, recovers the cold energy, returns to the gas compressor and continues to participate in liquefaction.
In some preferred embodiments, the mixed working medium refrigerating unit further comprises a pre-cooling cycle for pre-cooling the high-pressure feed gas and the mixed working medium; the pre-cooling cycle can adopt the configurations of a vapor compression refrigeration cycle, an absorption refrigeration cycle, a commercial water chilling unit and the like.
In some preferred embodiments, the liquefied gas formed by cooling the high-pressure feed gas by the mixed working medium refrigerator unit is firstly subcooled to-150 ℃ to-190 ℃ by the low-pressure steam through the subcooling heat exchanger, then is divided into a small part of liquefied gas through the gas distributor, the small part of liquefied gas is throttled to near normal pressure by the main throttling element and is cooled to below-152 ℃ to-192 ℃, enters the subcooling heat exchanger to provide cold energy and is gasified to form low-pressure steam, and then is reheated by the mixed working medium refrigerator unit and returns to the gas compressor after recovering the cold energy to continue to participate in liquefaction; and the residual liquefied gas separated by the gas distributor enters the liquid storage tank through the throttling of the liquefied gas throttling element to obtain the supercooled liquid.
In some preferred embodiments, the subcooling unit further comprises a first liquefied gas throttling element; the high-pressure feed gas is cooled by the mixed working medium refrigerating unit to form liquefied gas, the liquefied gas is subcooled to-150 ℃ to-190 ℃ by the low-pressure steam through the subcooling heat exchanger, the liquefied gas is throttled to certain optimized intermediate pressure by the first throttling element and then enters the gas-liquid separator, the separated gas phase is further throttled to near normal pressure by the main throttling element and is cooled to the temperature below-152 ℃ to-192 ℃ to form low-pressure steam, the low-pressure steam enters the subcooling heat exchanger to provide cold energy, and then the low-pressure steam is reheated by the mixed working medium refrigerating unit and returns to the gas compressor after recovering the cold energy to continuously participate in liquefaction; and throttling the liquid phase separated by the gas-liquid separator into the liquid storage tank by the liquefied gas throttling element to obtain the supercooled liquid.
In some preferred embodiments, the liquefied gas formed by cooling the high-pressure feed gas by the mixed working medium refrigerating unit is subcooled to-150 ℃ to-190 ℃ by the low-pressure vapor through the subcooling heat exchanger, and then is directly throttled to the storage pressure and enters the storage tank to obtain a subcooled liquid; the separated flash vapor enters a supercooling heat exchanger to provide cold energy, and finally returns to the gas pressurization unit after the cold energy is recovered by the mixed working medium refrigerating unit to continuously participate in liquefaction;
the invention adopts the technical scheme that the method has the advantages that:
the mixed working medium high-pressure gas liquefaction and supercooling system provided by the invention adopts a mixed working medium throttling refrigeration technology to perform distributed cooling on high-pressure gas, has high cold energy utilization efficiency, performs supercooling by utilizing liquefied gas, avoids serious efficiency attenuation caused by low refrigeration temperature of a mixed working medium refrigerator, has a relatively simple flow structure and does not need an additional supercooling refrigerator.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system provided in embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system provided in embodiment 2 of the present invention.
Fig. 3 is a schematic structural diagram of a supercooling unit according to embodiment 3 of the present invention.
Fig. 4 is a schematic structural diagram of a supercooling unit according to embodiment 4 of the present invention.
Fig. 5 is a schematic structural diagram of a supercooling unit according to embodiment 5 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, a mixed working medium high-pressure gas liquefying and supercooling system according to embodiment 1 of the present invention includes: the system comprises a gas pressurization unit 1, a mixed working medium refrigerating unit 2 and a supercooling unit 3. Wherein:
the gas booster unit 1 comprises a gas compressor 101 and an after cooler 102.
It can be understood that the low-pressure feed gas and the low-pressure steam can be mixed by a multi-stage compressor and then pressurized to 10-30 bar.
The mixed working medium refrigerating unit 2 comprises a mixed working medium main cooling cycle 21.
The subcooling unit 3 comprises a distributor 301, a subcooling heat exchanger 302, a main throttling element 303, a liquid storage tank 304 and a liquefied gas throttling element 305.
The working mode of the mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 1 of the invention is as follows:
the low-pressure feed gas is pressurized by the gas compressor 101 to form a high-pressure feed gas, the high-pressure feed gas enters the mixed working medium refrigerating unit 2 and is cooled and liquefied by the mixed working medium main cooling cycle 21 to form liquefied gas, and then the liquefied gas enters the supercooling unit 3.
The liquefied gas is divided into two parts by the distributor 301, one part of the high-pressure liquefied feed gas enters the supercooling heat exchanger 302 and is supercooled to-150 ℃ to-190 ℃ by the low-pressure steam, and the supercooled liquefied gas is throttled by the liquefied gas throttling element 305 and enters the liquid storage tank to obtain supercooled liquid; the other part of the high-pressure liquefied raw gas is throttled to near normal pressure by the liquefied gas main throttling element 303, cooled to a temperature below-152 ℃ to-192 ℃, enters the supercooling heat exchanger 302 to provide cold energy and is gasified to form low-pressure steam, and then returns to the gas compressor 101 after being reheated by the mixed working medium refrigerating unit 2 and recovering the cold energy to continuously participate in liquefaction.
The mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 1 of the invention adopts a mixed working medium throttling refrigeration technology to perform distributed cooling on high-pressure gas, has high cold energy utilization efficiency, utilizes liquefied gas to perform supercooling, avoids serious efficiency attenuation caused by too low refrigeration temperature of a mixed working medium refrigerator, has a relatively simple flow structure, and does not need an additional supercooling refrigerator.
Example 2
Referring to fig. 2, a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system according to embodiment 2 of the present invention is shown, and for convenience of description, only related drawings are described below.
The difference from the embodiment 1 is that the mixed working medium refrigerating unit provided by the embodiment 2 of the present invention further includes a pre-cooling cycle 22 for pre-cooling the high-pressure raw material gas and the mixed working medium; the pre-cooling cycle 22 may be configured as a vapor compression refrigeration cycle, an absorption refrigeration cycle, a commercial chiller, or the like.
Other working modes can refer to embodiment 1, and are not described herein.
The mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 2 of the invention adopts precooling circulation, so that the capacity of the system for adapting to higher environmental temperature is improved, and the liquefaction energy consumption can be reduced.
Example 3
Fig. 3 is a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system according to embodiment 4 of the present invention.
The liquefied gas formed by cooling the high-pressure feed gas by the mixed working medium refrigerating unit 2 is firstly subcooled to-150 ℃ to-190 ℃ by the subcooling heat exchanger 302, then a small strand of liquefied gas is separated by the gas distributor 301, the small strand of liquefied gas is throttled to near normal pressure by the main throttling element 303, cooled to the temperature of-152 ℃ to-192 ℃ or below, enters the subcooling heat exchanger 302 for gasification to provide cold energy and form low-pressure steam, and then is reheated by the mixed working medium refrigerating unit 2, returns to the gas compressor 101 after recovering the cold energy, and continuously participates in liquefaction;
the remaining liquefied gas branched off by the gas distributor 301 is throttled by the liquefied gas throttling element 305 into the liquid storage tank 304 to obtain a subcooled liquid.
Other working modes can refer to embodiment 1, and are not described herein.
The mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 3 of the invention utilizes the liquefied gas to perform supercooling, avoids the serious efficiency attenuation caused by the excessively low refrigerating temperature of the mixed working medium refrigerator, has a relatively simple flow structure and does not need an additional supercooling refrigerator.
Example 4
Fig. 4 is a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system according to embodiment 4 of the present invention.
The difference from embodiment 1 above is that the subcooling unit 3 further includes a gas-liquid separator 306, a first liquefied gas throttling element 307; wherein:
the liquefied gas formed by cooling the high-pressure feed gas by the mixed working medium refrigerating unit 2 is subcooled to-150 ℃ to-190 ℃ by the subcooling heat exchanger 302, throttled to a certain optimized intermediate pressure by the first liquefied gas throttling element 307 and then enters the gas-liquid separator 306, the separated gas phase is throttled to near normal pressure by the main throttling element 303, cooled to a temperature below-152 ℃ to-192 ℃, enters the subcooling heat exchanger 302 to provide cold energy, is reheated by the mixed working medium refrigerating unit 2, recovers the cold energy, returns to the gas compressor 101 and continues to participate in liquefaction;
the liquid phase separated by the gas-liquid separator 306 is throttled by the liquefied gas throttling element 305 and enters the liquid storage tank 304 to obtain a subcooled liquid.
Other working modes can refer to embodiment 1, and are not described herein.
The mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 4 of the invention utilizes the liquefied gas to perform supercooling, avoids the serious efficiency attenuation caused by the excessively low refrigerating temperature of the mixed working medium refrigerator, has a relatively simple flow structure and does not need an additional supercooling refrigerator.
Example 5
Fig. 5 is a schematic structural diagram of a mixed working medium high-pressure gas liquefaction and supercooling system according to embodiment 5 of the present invention.
The difference from the embodiment 1 is that the liquefied gas formed by cooling the high-pressure raw material gas by the mixed working medium refrigerator unit 2 is subcooled to-150 ℃ to-190 ℃ by the subcooling heat exchanger 302, then directly enters the liquid storage tank 304 after being throttled to storage pressure by the liquefied gas throttling element 305, and the separated flash vapor enters the subcooling heat exchanger 302 to provide cold energy, then is reheated by the mixed working medium refrigerator unit 2 and returns to the gas compressor 101 after recovering the cold energy, and then continuously participates in liquefaction;
the mixed working medium high-pressure gas liquefaction and supercooling system provided by the embodiment 5 of the invention utilizes the liquefied gas to perform supercooling, avoids the serious efficiency attenuation caused by the excessively low refrigerating temperature of the mixed working medium refrigerator, has a relatively simple flow structure, and does not need an additional supercooling refrigerator.
It is to be understood that various features of the above-described embodiments may be combined in any combination, and for the sake of brevity, all possible combinations of features in the above-described embodiments may not be described in detail, but rather, all combinations of features may be considered to fall within the scope of the present disclosure unless there is a conflict between such combinations.
Of course, the mixed working medium high-pressure gas liquefaction and supercooling system cathode material of the invention can also have various changes and modifications, and is not limited to the specific structure of the above embodiment. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.

Claims (5)

1.一种混合工质高压气体液化与过冷系统，其特征在于，包括：气体增压单元、混合工质制冷机单元、主冷箱单元和过冷单元，所述的气体增压单元包括气体压缩机与后冷却器，所述的混合工质制冷机单元包括混合工质主冷循环，所述的过冷单元包括分配器、过冷换热器、主节流元件、液化气体节流元件及储液罐，其中：1. A mixed working medium high-pressure gas liquefaction and subcooling system, characterized in that, comprising: a gas booster unit, a mixed working medium refrigerator unit, a main cold box unit and a subcooling unit, and the gas booster unit includes A gas compressor and an aftercooler, the mixed working medium refrigerator unit includes a mixed working medium main cooling cycle, and the subcooling unit includes a distributor, a subcooling heat exchanger, a main throttling element, and a liquefied gas throttle Components and reservoirs, including: 低压原料气经所述气体压缩机增压后进入所述后冷却器冷却，形成的高压原料气进入所述混合工质制冷机单元；The low-pressure raw material gas is pressurized by the gas compressor and then enters the aftercooler for cooling, and the formed high-pressure raw material gas enters the mixed working fluid refrigerator unit; 所述混合工质制冷机单元包括混合工质主冷循环，为气体液化提供制冷量；所述混合工质主冷循环采用一次节流循环、分离循环多种构型；The mixed working fluid refrigerator unit includes a mixed working fluid main refrigeration cycle, which provides refrigeration capacity for gas liquefaction; the mixed working fluid main refrigeration cycle adopts multiple configurations of a throttling cycle and a separation cycle; 在所述混合工质制冷机单元中冷却至低温并被液化的所述高压原料气被所述的分配器分为两部分，一部分所述高压液化原料气进入所述过冷换热器被低压蒸气过冷至-150℃～-190℃，过冷后的液化气体被所述液化气体节流元件节流进入所述储液罐，得到过冷液体；另一部分所述高压液化原料气经所述主节流元件节流至接近常压并降温至-152℃～-192℃以下后进入所述过冷换热器提供冷量并气化后形成低压蒸气，然后再经所述混合工质制冷机单元复温并回收冷量后返回至所述气体压缩机，继续参与液化。The high-pressure raw material gas cooled to low temperature and liquefied in the mixed refrigerant unit is divided into two parts by the distributor, and a part of the high-pressure liquefied raw material gas enters the subcooling heat exchanger and is low-pressure The vapor is supercooled to -150°C to -190°C, and the supercooled liquefied gas is throttled by the liquefied gas throttling element into the liquid storage tank to obtain a supercooled liquid; another part of the high-pressure liquefied raw material gas passes through the The main throttling element is throttled to close to normal pressure and cooled to below -152°C to -192°C, and then enters the subcooling heat exchanger to provide cooling capacity and gasifies to form low-pressure steam, which is then passed through the mixed working fluid. The refrigerator unit is rewarmed and the cold energy is recovered and returned to the gas compressor to continue to participate in liquefaction. 2.如权利要求1所述的混合工质高压气体液化与过冷系统，其特征在于，所述混合工质制冷机单元还包括预冷循环，对所述高压原料气和混合工质进行预冷；所述预冷循环采用蒸汽压缩制冷循环、吸收式制冷循环以及商用冷水机组构型。2. The mixed working fluid high-pressure gas liquefaction and subcooling system according to claim 1, wherein the mixed working fluid refrigerator unit further comprises a pre-cooling cycle for pre-cooling the high-pressure raw material gas and the mixed working fluid. cooling; the pre-cooling cycle adopts the configuration of a vapor compression refrigeration cycle, an absorption refrigeration cycle and a commercial chiller. 3.如权利要求1或2所述的混合工质高压气体液化与过冷系统，其特征在于，所述液化气体先经过所述过冷换热器再经过所述分配器，其中：3. The mixed working fluid high-pressure gas liquefaction and subcooling system according to claim 1 or 2, wherein the liquefied gas first passes through the subcooling heat exchanger and then passes through the distributor, wherein: 所述高压原料气经所述混合工质制冷机单元冷却形成的液化气体经所述过冷换热器被所述低压蒸气过冷至-150℃～-190℃，再经气体分配器分出一小股液化气体，该小股液化气体经所述主节流元件节流至接近常压并降温至-152℃～-192℃以下后进入所述过冷换热器提供冷量并气化后形成低压蒸气，然后再经所述混合工质制冷机单元复温并回收冷量后返回至所述气体压缩机，继续参与液化；The liquefied gas formed by the cooling of the high-pressure raw material gas by the mixed working fluid refrigerator unit is sub-cooled by the low-pressure steam to -150℃～-190℃ through the subcooling heat exchanger, and then separated through the gas distributor. A small stream of liquefied gas, which is throttled to near normal pressure through the main throttling element and cooled to below -152°C to -192°C, and then enters the subcooling heat exchanger to provide cooling capacity and gasify After that, low-pressure steam is formed, which is then rewarmed by the mixed working fluid refrigerator unit and the cold energy is recovered, and then returned to the gas compressor to continue to participate in liquefaction; 经所述分配器分出的剩余液化气体经所述液化气体节流元件节流进入所述储液罐，得到过冷液体。The remaining liquefied gas separated by the distributor is throttled through the liquefied gas throttling element into the liquid storage tank to obtain supercooled liquid. 4.如权利要求1或2所述的混合工质高压气体液化与过冷系统，其特征在于，所述过冷单元还包括第一液化气体节流元件；其中：4. The mixed working fluid high-pressure gas liquefaction and subcooling system according to claim 1 or 2, wherein the subcooling unit further comprises a first liquefied gas throttling element; wherein: 所述高压原料气经所述混合工质制冷机单元冷却形成的液化气体经所述过冷换热器被所述低压蒸气过冷至-150℃～-190℃，再经所述第一液化气体节流元件节流至某一优化的中间压力后进入气液分离器，分离出的气相经所述主节流元件进一步节流至接近常压并降温至-152℃～-192℃以下后形成低压蒸气进入所述过冷换热器提供冷量，然后再经所述混合工质制冷机单元复温并回收冷量后返回至所述气体压缩机，继续参与液化；The liquefied gas formed by the cooling of the high-pressure raw material gas by the mixed working fluid refrigerator unit is sub-cooled by the low-pressure steam through the sub-cooling heat exchanger to -150°C to -190°C, and then liquefied by the first liquefied gas. The gas throttling element is throttled to an optimized intermediate pressure and then enters the gas-liquid separator. The separated gas phase is further throttled to near normal pressure through the main throttling element and cooled to below -152℃～-192℃ The low-pressure vapor is formed into the subcooling heat exchanger to provide cooling capacity, and then rewarmed by the mixed working fluid refrigerator unit and the cooling capacity is recovered and returned to the gas compressor to continue to participate in liquefaction; 经所述气液分离器分出的液相经所述液化气体节流元件节流进入所述储液罐，得到过冷液体。The liquid phase separated by the gas-liquid separator is throttled through the liquefied gas throttling element into the liquid storage tank to obtain supercooled liquid. 5.根据权利要求1或2所述的一种混合工质高压气体液化与过冷系统，其特征在于，所述高压原料气经所述混合工质制冷机单元冷却形成的液化气体经所述过冷换热器被所述低压蒸气过冷至-150℃～-190℃，然后直接被节流至储存压力后进入储罐，得到过冷液体；分离出的闪蒸气进入过冷换热器提供冷量，最后在混合工质制冷机单元回收冷量后返回气体增压单元，继续参与液化。5. A mixed working fluid high-pressure gas liquefaction and subcooling system according to claim 1 or 2, wherein the liquefied gas formed by cooling the high-pressure raw material gas through the mixed working fluid refrigerator unit passes through the The subcooling heat exchanger is subcooled by the low pressure steam to -150℃～-190℃, and then directly throttled to the storage pressure and then enters the storage tank to obtain the subcooled liquid; the separated flash steam enters the subcooled heat exchanger Provide cold energy, and finally return to the gas booster unit after the cold energy is recovered by the mixed working medium refrigerator unit, and continue to participate in liquefaction.
CN202010090159.2A 2020-02-13 2020-02-13 Mixed working medium high-pressure gas liquefaction and supercooling system Active CN111238163B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010090159.2A CN111238163B (en) 2020-02-13 2020-02-13 Mixed working medium high-pressure gas liquefaction and supercooling system

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010090159.2A CN111238163B (en) 2020-02-13 2020-02-13 Mixed working medium high-pressure gas liquefaction and supercooling system

Publications (2)

Publication Number Publication Date
CN111238163A CN111238163A (en) 2020-06-05
CN111238163B true CN111238163B (en) 2021-12-17

Family

ID=70870532

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010090159.2A Active CN111238163B (en) 2020-02-13 2020-02-13 Mixed working medium high-pressure gas liquefaction and supercooling system

Country Status (1)

Country Link
CN (1) CN111238163B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3130018B1 (en) * 2021-12-06 2024-04-19 Engie Process for liquefying a gas to be treated rich in methane, and corresponding installation
EP4662447A1 (en) * 2023-02-10 2025-12-17 Airco Process Technology A/S Small scale expansion cycle methane liquefaction process

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462861A (en) * 2002-05-27 2003-12-24 中国科学院理化技术研究所 Method for cooling industrial gas from ambient temperature to cryogenic temperature and obtaining liquefaction
CN101967413A (en) * 2010-06-07 2011-02-09 杭州福斯达实业集团有限公司 Method and device for liquefying natural gas via refrigeration of single mixed refrigerant
CN202328997U (en) * 2011-11-18 2012-07-11 新地能源工程技术有限公司 Device for refrigerating liquefied natural gas by adopting single mixed working medium
CN202522014U (en) * 2012-03-31 2012-11-07 贾林祥 Mini double-mixed refrigerant liquefying device for MiniDMR
CN103398545A (en) * 2013-07-29 2013-11-20 中国科学院理化技术研究所 System for producing liquefied natural gas by multistage pressure throttling of feed gas
CN104792114A (en) * 2015-04-10 2015-07-22 四川金科深冷设备工程有限公司 BOG re-liquefaction process and re-liquefaction recovery system thereof
CN204757541U (en) * 2015-06-09 2015-11-11 杭州福斯达实业集团有限公司 Single cryogenic natural gas liquefaction device of cryogen that mixes
CN107850264A (en) * 2015-07-31 2018-03-27 国际壳牌研究有限公司 Method and system for processing a liquefied natural gas stream at an LNG import terminal
CN108027199A (en) * 2015-08-06 2018-05-11 乔治洛德方法研究和开发液化空气有限公司 Method for producing liquefied natural gas
CN109084526A (en) * 2018-07-23 2018-12-25 中国科学院理化技术研究所 VOCs liquefaction recovery system

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462861A (en) * 2002-05-27 2003-12-24 中国科学院理化技术研究所 Method for cooling industrial gas from ambient temperature to cryogenic temperature and obtaining liquefaction
CN101967413A (en) * 2010-06-07 2011-02-09 杭州福斯达实业集团有限公司 Method and device for liquefying natural gas via refrigeration of single mixed refrigerant
CN202328997U (en) * 2011-11-18 2012-07-11 新地能源工程技术有限公司 Device for refrigerating liquefied natural gas by adopting single mixed working medium
CN202522014U (en) * 2012-03-31 2012-11-07 贾林祥 Mini double-mixed refrigerant liquefying device for MiniDMR
CN103398545A (en) * 2013-07-29 2013-11-20 中国科学院理化技术研究所 System for producing liquefied natural gas by multistage pressure throttling of feed gas
CN104792114A (en) * 2015-04-10 2015-07-22 四川金科深冷设备工程有限公司 BOG re-liquefaction process and re-liquefaction recovery system thereof
CN204757541U (en) * 2015-06-09 2015-11-11 杭州福斯达实业集团有限公司 Single cryogenic natural gas liquefaction device of cryogen that mixes
CN107850264A (en) * 2015-07-31 2018-03-27 国际壳牌研究有限公司 Method and system for processing a liquefied natural gas stream at an LNG import terminal
CN108027199A (en) * 2015-08-06 2018-05-11 乔治洛德方法研究和开发液化空气有限公司 Method for producing liquefied natural gas
CN109084526A (en) * 2018-07-23 2018-12-25 中国科学院理化技术研究所 VOCs liquefaction recovery system

Also Published As

Publication number Publication date
CN111238163A (en) 2020-06-05

Similar Documents

Publication Publication Date Title
CA2618576C (en) Natural gas liquefaction process for lng
CN101608860B (en) Gas liquefying process for mixed refrigerant and mixed refrigerant
KR101099079B1 (en) Cryogenic liquefying refrigerating method and device
JP2001165562A (en) Method of liquefying source gas
WO2019071869A1 (en) Device and method using stepped cooling to recover ethane from natural gas
MX2013014870A (en) Process for liquefaction of natural gas.
CN110186251B (en) Three-cycle natural gas liquefaction device and method suitable for ultra-large scale
CN112066642B (en) A system for liquefying high nitrogen and helium-containing natural gas and extracting crude helium and nitrogen
TW202328612A (en) Hydrogen liquefaction with stored hydrogen refrigeration source
CN111238163B (en) Mixed working medium high-pressure gas liquefaction and supercooling system
CA2914848C (en) Systems and methods for natural gas liquefaction capacity augmentation
CN106595220B (en) Liquefaction system for liquefying natural gas and liquefaction method thereof
CN101614464B (en) Method for liquefying natural gas through double-expansion of high-temperature and low-temperature nitrogen gas
CN203310202U (en) Dual-mixed-refrigerant liquefying system applied to base load type natural gas liquefaction factory
KR20110076214A (en) Gas liquefaction method
CN110160315B (en) Liquid air separation device utilizing low-cost night electric power and production method
CN115682628A (en) Hydrogen liquefaction system and process based on mixed refrigerant precooling
CN102564061A (en) Two-stage mixed refrigerant circulation liquefaction system applied to base load type natural gas liquefaction factory
CN103234326B (en) Be applied to two azeotrope liquefaction systems of base lotus type natural gas liquefaction plant
CN202692600U (en) Two-stage mixing refrigerant cycle gas liquification system
CN218202216U (en) A high-yield dry ice production device
US10330381B2 (en) Plant for the liquefaction of nitrogen using the recovery of cold energy deriving from the evaporation of liquefied natural gas
US20250347463A1 (en) Installation comprising lng and renewable electricity facilities with at least one thermal energy storage system
CN216522650U (en) Liquid oxygen liquefaction air separation plant
US20230213273A1 (en) Integrated industrial unit

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant