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CN112212610A - A kind of method for preparing liquid hydrogen from LNG - Google Patents

A kind of method for preparing liquid hydrogen from LNG Download PDF

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Publication number
CN112212610A
CN112212610A CN202011299737.XA CN202011299737A CN112212610A CN 112212610 A CN112212610 A CN 112212610A CN 202011299737 A CN202011299737 A CN 202011299737A CN 112212610 A CN112212610 A CN 112212610A
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China
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hydrogen
cooling
lng
section
heat
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CN202011299737.XA
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CN112212610B (en
Inventor
王秀林
李又武
张瑜
侯海龙
张丹
宋鹏飞
姚辉超
穆祥宇
隋依言
王斯
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China National Offshore Oil Corp CNOOC
CNOOC Gas and Power Group Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Gas and Power Group Co Ltd
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    • 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
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    • 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
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
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    • 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
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    • F25J1/0214—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 as a dual level refrigeration cascade with at least one MCR cycle
    • F25J1/0215—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 as a dual level refrigeration cascade with at least one MCR cycle with one SCR cycle
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    • 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
    • F25J1/0229—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
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    • 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
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0262—Details of the cold heat exchange system
    • F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • F25J1/0265—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
    • F25J1/0268—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer using a dedicated refrigeration means
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    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
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    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
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    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
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Abstract

本发明公开了一种LNG制备液氢的方法。所述方法包括如下步骤：增压后的LNG与H2与He的混合物换热后，进入预冷单元与氮气或混合冷剂进行换热并升温；升温后的天然气经加热后进入天然气转化工段；在天然气转化工段内，天然气经转化、变换和变压吸附提浓得到富氢气体；富氢气体经压缩工段增压后，进入氢气预冷段，与氮气或混合冷剂进行换热冷却；经氢气预冷段冷却后的氢气进入氢气液化段与He/Ne混合物进行换热冷却，经节流阀节流后，制得液氢。本发明直接将LNG气化工艺与氢气液化工艺能量相互利用，制备的液氢可方便进行运输和利用，提高氢气的运输消耗和氢气经济性，流程简单、自动化程度高，所采用的设备可靠，提高氢气的制备成本和液化成本，经济效益显著。The invention discloses a method for preparing liquid hydrogen from LNG. The method includes the following steps: after the pressurized LNG and the mixture of H 2 and He exchange heat, enter the pre-cooling unit to exchange heat with nitrogen or mixed refrigerant and heat up; the heated natural gas enters the natural gas conversion section after being heated ; In the natural gas conversion section, the natural gas is converted, transformed, and concentrated by pressure swing adsorption to obtain hydrogen-rich gas; after the hydrogen-rich gas is pressurized in the compression section, it enters the hydrogen pre-cooling section, and exchanges heat with nitrogen or mixed refrigerant for cooling; The hydrogen cooled in the hydrogen pre-cooling section enters the hydrogen liquefaction section for heat exchange cooling with the He/Ne mixture, and after being throttled by a throttle valve, liquid hydrogen is produced. The invention directly utilizes the energy of the LNG gasification process and the hydrogen liquefaction process, the prepared liquid hydrogen can be conveniently transported and utilized, the transportation consumption of hydrogen and the hydrogen economy are improved, the process is simple, the degree of automation is high, and the equipment used is reliable. The cost of hydrogen production and liquefaction is increased, and the economic benefits are significant.

Description

Method for preparing liquid hydrogen from LNG
Technical Field
The invention relates to a method for preparing liquid hydrogen by LNG.
Background
Hydrogen energy is a recognized clean energy source, is considered as the most potential fossil fuel substitute in the future due to the advantages of high energy density, zero carbon emission and the like, is considered as an ultimate scheme in the field of mobile energy represented by hydrogen fuel cell automobiles, and green hydrogen can also be used as a hydrogen source in the hydrogenation process of fossil resources to realize carbon emission reduction. The hydrogen energy is expected to be mainly demonstrated in an industrial chain in 2020, 1000 hydrogen energy stations are built in the initial scale in 2030 years of the hydrogen energy industrial chain (including hydrogen production, hydrogen storage and transportation, hydrogen stations, fuel cell vehicles, distributed energy sources and the like), the infrastructure of the hydrogen energy is improved in 2050, the hydrogen energy and the fuel cell are popularized and applied in the fields of transportation, distributed energy sources and the like, and 10000 hydrogen energy stations are built, so that the hydrogen energy becomes an important component of the energy structure in China. .
Due to the major breakthrough of fuel cell technology and the rapid reduction of cost, the global hydrogen energy industry develops rapidly in recent years, and major countries in the world develop strategies of the hydrogen energy industry one after another, and national subsidy policies are issued in a targeted manner for each industrial chain link of the hydrogen energy. At present, the key factor influencing the development of the hydrogen energy industry is the price of hydrogen, and the price of hydrogen determines the economy of hydrogen utilization, and further determines the economy and feasibility of the whole industry. The hydrogen energy industry comprises three main links of hydrogen production, hydrogen storage and transportation and hydrogen utilization, wherein the key for realizing the development of the hydrogen energy industry is the high-efficiency hydrogen production technology and reducing the hydrogen operation cost.
Disclosure of Invention
Aiming at the problems of high energy consumption and liquid hydrogen manufacturing cost of hydrogen liquefaction, the invention provides a method for liquefying hydrogen by using LNG cold energy, and the concentration of the obtained hydrogen is more than 99.9 percent; the invention mutually utilizes the energy of the LNG gasification process and the hydrogen liquefaction process, has simple process, high automation degree and convenient operation, and can well solve the problem of energy consumption of hydrogen liquefaction.
Specifically, the method for preparing liquid hydrogen by using LNG provided by the invention comprises the following steps:
1) pressurized LNG and H2After exchanging heat with the mixture of He, entering a precooling unit to exchange heat with nitrogen or mixed refrigerant and heating;
2) heating the heated natural gas and then entering a natural gas conversion section;
3) in the natural gas conversion section, the natural gas is subjected to conversion, transformation and pressure swing adsorption concentration to obtain hydrogen-rich gas;
4) after being pressurized by a compression section, the hydrogen-rich gas enters a hydrogen pre-cooling section and exchanges heat with nitrogen or mixed refrigerant for cooling;
5) and the hydrogen cooled by the hydrogen pre-cooling section enters a hydrogen liquefying section to exchange heat with the He/Ne mixture for cooling, and the liquid hydrogen is obtained after throttling by a throttling valve.
In the method, in the step 1), the LNG is pressurized to 0.3-10 MPaG by adopting a low-temperature LNG booster pump;
and heating the LNG to-100-0 ℃.
In the method, in the step 1), the nitrogen or the mixed refrigerant is pressurized to 0.5-5 MPAG, then exchanges heat with the LNG, is cooled to-180-10 ℃, and is throttled, exchanges heat with the hydrogen in the step 4), and then is continuously pressurized for recycling.
In the method, in the step 2), the natural gas is heated to 600-1000 ℃;
in the step 3), the concentration of hydrogen in the hydrogen-rich gas is more than 99.9%.
In the method, in the step 5), in the hydrogen liquefaction section, the He/Ne mixture is cooled after being pressurized and subjected to heat exchange with low-temperature nitrogen, the cooled He/Ne mixture is throttled to 0.1-2 MPaG and then subjected to heat exchange with hydrogen, and the hydrogen is cooled to-254-170 ℃ and the pressure is 0.02-4 MPAG.
In the above method, in step 5), the concentration of Ne in the He/Ne mixture is in the range of 5% to 30%.
In the above method, the mixed refrigerant is N2、C2H4And CH4The concentration of the mixed gas is 10-90%, 5-50% and 5-40% respectively.
The method directly and mutually utilizes the energy of the LNG gasification process and the hydrogen liquefaction process, the prepared liquid hydrogen can be conveniently transported and utilized, the transportation consumption and the hydrogen economy of the hydrogen are improved, the method has simple flow and high automation degree, the adopted equipment is reliable, the preparation cost and the liquefaction cost of the hydrogen are improved, and the economic benefit is obvious.
Drawings
Fig. 1 is a schematic flow diagram of the LNG-to-liquid hydrogen process of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment, LNG enters after being pressurized
The nitrogen (or mixed refrigerant) cooling unit exchanges heat with low-temperature refrigerant hydrogen, and after heat exchange, natural gas is heated and enters a natural gas conversion working section to be converted into hydrogen-rich gas; concentrating the hydrogen-rich gas in a pressure swing adsorption section; after entering a pressurizing unit for pressurizing and cooling, entering a deep cooling unit for cooling; and hydrogen at the outlet of the cryogenic unit enters a hydrogen cryogenic section to exchange heat with the He/Ne mixture, is throttled by a throttle valve and then enters a liquid hydrogen storage tank.
Examples 1,
(1) Pressurized LNG (7MPaG) and (H)2And + He) heat exchange, then entering a precooling unit to exchange heat with low-temperature refrigerant and heating to-20 ℃ (material flow 2-4-5-6).
(2) And heating the heated natural gas to 820 ℃ by a combustion furnace, and then feeding the heated natural gas into a natural gas conversion section (material flow 6-7).
(3) In the natural gas conversion section, after natural gas is converted, transformed and subjected to pressure swing adsorption concentration, a hydrogen-rich gas mixture (material flow 7-9-10-12-14) with the hydrogen concentration of more than 99.9% is prepared.
(4) And pressurizing the hydrogen-rich gas mixture by a compression section for 3.0MPAG, cooling the hydrogen-rich gas mixture in a hydrogen cooling section, and performing heat exchange between a cryogenic unit and low-temperature refrigerant nitrogen to-155 ℃ (material flow is 14-16-17-19-20).
(5) The hydrogen cooled by the cryogenic unit enters a hydrogen liquefaction section to be subjected to heat exchange cooling with a He/Ne mixture (the concentration of Ne is 40%), and the cooling temperature is-248 ℃ (material flow is 20-21).
(6) And (3) throttling the hydrogen cooled by the hydrogen liquefaction working section to 0.1MPaG by a throttle valve, and then carrying out a hydrogen storage tank (material flow 17-22).
Examples 2,
(1) Pressurized LNG (5MPaG) and (H)2And + He) heat exchange, then entering a precooling unit to exchange heat with the low-temperature mixed refrigerant and heating to-40 ℃ (material flow 2-4-5-6).
(2) The heated natural gas is heated to 900 ℃ by a combustion furnace and then enters a natural gas conversion section (material flow 6-7).
(3) In the natural gas conversion section, after natural gas is converted, transformed and subjected to pressure swing adsorption concentration, a hydrogen-rich gas mixture (stream 7-8-10-14) with the hydrogen concentration of more than 99.9% is prepared.
(4) The hydrogen-rich gas mixture is pressurized by 3.0MPAG in the compression section, enters a hydrogen cooling section for cooling, and is subjected to a deep cooling unit and a low-temperature refrigerant mixture (N)2(50mol％)、C2H4(20mol％)、CH4(15 mol%) and C3H8(15 mol%)) was heat exchanged to-158 deg.c (stream 28-26-8-29-27).
(5) The hydrogen cooled by the cryogenic unit enters a hydrogen liquefaction section to exchange heat with a He/Ne mixture (Ne concentration is 40) for cooling at the temperature of-250 ℃ (material flow is 20-23).
(6) And the hydrogen cooled by the hydrogen liquefaction working section is throttled to 0.08MPaG by a throttle valve to prepare liquid hydrogen (material flow 21-22).

Claims (8)

1.一种LNG制备液氢的方法，包括如下步骤：1. a method for preparing liquid hydrogen from LNG, comprising the steps: 1)增压后的LNG与H2与He的混合物换热后，进入预冷单元与氮气或混合冷剂进行换热并升温；1) After the pressurized LNG and the mixture of H 2 and He exchange heat, enter the pre-cooling unit to exchange heat with nitrogen or mixed refrigerant and heat up; 2)升温后的天然气经加热后进入天然气转化工段；2) The heated natural gas enters the natural gas conversion section after being heated; 3)在所述天然气转化工段内，所述天然气经转化、变换和变压吸附提浓得到富氢气体；3) in the natural gas conversion section, the natural gas is converted, shifted and enriched by pressure swing adsorption to obtain hydrogen-rich gas; 4)所述富氢气体经压缩工段增压后，进入氢气预冷段，与氮气或混合冷剂进行换热冷却；4) After the hydrogen-rich gas is pressurized in the compression section, it enters the hydrogen pre-cooling section, and exchanges heat with nitrogen or mixed refrigerant for cooling; 5)经所述氢气预冷段冷却后的氢气进入氢气液化段与He/Ne混合物进行换热冷却，经节流阀节流后，制得液氢。5) The hydrogen cooled in the hydrogen pre-cooling section enters the hydrogen liquefaction section for heat exchange cooling with the He/Ne mixture, and after being throttled by a throttle valve, liquid hydrogen is obtained. 2.根据权利要求1所述的方法，其特征在于：步骤1)中，采用低温LNG增压泵将所述LNG增压至0.3～10MPaG；2. The method according to claim 1, characterized in that: in step 1), a low-temperature LNG booster pump is used to pressurize the LNG to 0.3-10MPaG; 所述LNG升温至-100～0℃。The LNG is heated to -100~0°C. 3.根据权利要求1或2所述的方法，其特征在于：步骤1)中，所述氮气或所述混合冷剂增压至0.5～5MPAG后与所述LNG换热被冷却至-180～10℃，经冷却后的氮气或混合冷剂节流后与步骤4)中的氢气换热后继续增压而循环使用。3. The method according to claim 1 or 2, wherein in step 1), the nitrogen gas or the mixed refrigerant is pressurized to 0.5-5 MPAG and then cooled to -180- At 10°C, the cooled nitrogen or mixed refrigerant is throttled and then heat-exchanged with the hydrogen in step 4), and then pressurized and recycled. 4.根据权利要求1-3中任一项所述的方法，其特征在于：步骤2)中，将所述天然气加热至600℃～1000℃；4. The method according to any one of claims 1-3, characterized in that: in step 2), the natural gas is heated to 600°C to 1000°C; 步骤3)中，所述富氢气体中氢气的浓度大于99.9％。In step 3), the concentration of hydrogen in the hydrogen-rich gas is greater than 99.9%. 5.根据权利要求1-4中任一项所述的方法，其特征在于：步骤4)中，所述氢气预冷段采用N2或混合冷剂进行冷却。5. The method according to any one of claims 1-4, characterized in that: in step 4), the hydrogen pre-cooling section adopts N 2 or mixed refrigerant for cooling. 6.根据权利要求1-5中任一项所述的方法，其特征在于：步骤5)中，所述氢气液化段中，所述He/Ne混合物增压后与LNG换热后进行冷却，冷却后的He/Ne混合物节流至0.1～2MPaG后，与氢气换热，将氢气冷却至-254℃～-170℃。6. The method according to any one of claims 1-5, wherein in step 5), in the hydrogen liquefaction section, the He/Ne mixture is pressurized and then cooled after exchanging heat with LNG, The cooled He/Ne mixture is throttled to 0.1-2 MPaG, and then heat-exchanged with hydrogen, and the hydrogen is cooled to -254°C to -170°C. 7.根据权利要求1-6中任一项所述的方法，其特征在于：步骤5)中，所述He/Ne混合物中Ne的浓度范围为5％～30％。7 . The method according to claim 1 , wherein in step 5), the concentration of Ne in the He/Ne mixture ranges from 5% to 30%. 8 . 8.根据权利要求1-6中任一项所述的方法，其特征在于：所述混合冷剂为N2、C2H4和CH4的混合气，浓度分别为10％～90％、5％～50％和5％～40％。8 . The method according to claim 1 , wherein the mixed refrigerant is a mixture of N 2 , C 2 H 4 and CH 4 , and the concentrations are 10% to 90%, 5% to 50% and 5% to 40%.
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