CN103697659B - The device and method of liquefied natural gas and rich hydrogen production is produced from high methane gas - Google Patents

The device and method of liquefied natural gas and rich hydrogen production is produced from high methane gas Download PDF

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CN103697659B
CN103697659B CN201310715495.1A CN201310715495A CN103697659B CN 103697659 B CN103697659 B CN 103697659B CN 201310715495 A CN201310715495 A CN 201310715495A CN 103697659 B CN103697659 B CN 103697659B
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heat exchanger
gas
cold
liquid
nitrogen
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CN201310715495.1A
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CN103697659A (en
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侯智德
丁友胜
蒋旭
施晓俊
王第珲
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中空能源设备有限公司
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0257Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/74Refluxing the column with at least a part of the partially condensed overhead gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/04Recovery of liquid products
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/12External refrigeration with liquid vaporising loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/18External refrigeration with incorporated cascade loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/42Quasi-closed internal or closed external nitrogen refrigeration cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/66Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34Details about subcooling of liquids

Abstract

The present invention relates to a kind of device and method producing liquefied natural gas and rich hydrogen production from high methane gas.Device comprises azeotrope compressor refrigeration system, chilldown system, liquefaction cold box system, nitrogen compressor system; Method comprise azeotrope cyclic process, high methane gas liquefaction and separation process, nitrogen refrigerant cycle process.The low temperature nitrogen of the low temperature hydrogen-rich gas that rectifying column of the present invention produces, nitrogen-rich gas and condenser external liquid nitrogen vaporization be used for cold enter liquid nitrogen before condenser/evaporator, be different from traditional supercooled liquid natural gas, the cold fluid of whole heat exchanger process and the heat exchange curve of hot fluid more mate, and heat exchanger cold-end temperature difference is less, therefore heat exchange efficiency is higher, energy consumption is lower.

Description

The device and method of liquefied natural gas and rich hydrogen production is produced from high methane gas

Technical field

The present invention relates to a kind of device and method producing liquefied natural gas and rich hydrogen production from high methane gas.

Background technology

Enriched Gas comparatively commonly coke-stove gas improves calorific value by methanation reaction, make most carbon monoxide, carbon dioxide conversion becomes methane, the methane volumetric mark that the synthesis gas of gained obtains after the purification that water washing de-oiling is washed after naphthalene, desulfurization is again more than 40 ~ 50%, is separately rich in hydrogen and nitrogen.High methane gas prepares LNG and rich hydrogen production through low-temperature liquefaction, cryogenic rectification again.The coke-stove gas being the richest in alkanisation is separated and prepares through purification, liquefaction the problem that liquefied natural gas not only can alleviate domestic natural gas shortage, and technological progress and the industry development of coking and energy industry can be promoted, development coke-stove gas LNG project can produce obvious economic benefit, environmental benefit and social benefit, recycles industry significant to coke-stove gas.

High methane gas and conventional gas form larger difference, and nitrogen, hydrogen content are relatively high, therefore liquefaction and separating technology is more complicated, energy consumption of unit product is higher.

Traditional hybrid refrigeration associating liquid nitrogen refrigerating produces the technique of liquefied natural gas and rich hydrogen production from high methane gas, the low temperature nitrogen that the low temperature hydrogen rich gas that rectifying column produces, rich nitrogen and condenser produce provides cold in two ways: one returns main heat exchanger for all hot-fluid stocks to provide cold, and a kind of is for crossing the liquefied natural gas distillated at the bottom of cold rectifying column.

Application number is 201210065876.5, name is called dehydrogenation nitrogen from high methane gas and produce the technique of liquefied natural gas and the Chinese patent of device, application number is 201110291609.5, name is called dehydrogenation from high methane gas, nitrogen, carbon monoxide produce the Chinese patent of the technique of liquefied natural gas, these prior aries still Shortcomings in refrigeration, high methane gas liquefaction and separating effect etc., specific energy consumption is higher, and deficiency is produced to hydrogen-rich gas, easily cause waste.

Summary of the invention

The object of the invention is to overcome above shortcomings in prior art, and a kind of reasonable in design, energy-conservation, device and method producing liquefied natural gas and rich hydrogen production from high methane gas that cost is low is provided.

The present invention's adopted technical scheme that solves the problem is: a kind of device producing liquefied natural gas and rich hydrogen production from high methane gas, comprises azeotrope compressor refrigeration system, chilldown system, liquefaction cold box system, nitrogen compressor system; Described azeotrope compressor refrigeration system comprises azeotrope compressor, an intercooler, aftercooler, a middle knockout drum; Azeotrope compressor has compression one section and compression two sections; Described chilldown system comprises precool heat exchanger device, cryogen gas-liquid separator; Described liquefaction cold box system comprises cooling heat exchanger, liquefaction heat exchanger, liquid nitrogen cross cold heat exchanger, denitrogenation rectifying column, dehydrogenation rectifying column; The tower top of dehydrogenation rectifying column is provided with an overhead condensation evaporimeter and a tower overhead gas liquid/gas separator; Be provided with tower bottom reboiler at the bottom of the tower of denitrogenation rectifying column, tower top is provided with No. two overhead condensation evaporimeters and No. two tower overhead gas liquid/gas separators; Described nitrogen compressor refrigeration system comprises nitrogen compressor, No. two intercoolers, No. two aftercoolers;

Compression one section, intercooler, middle knockout drum, the compression two sections of azeotrope compressor, aftercooler, the hot fluid section of precool heat exchanger device, a compound import for cryogen gas-liquid separator of azeotrope compressor are connected successively; The hot fluid section of the gas vent of cryogen gas-liquid separator, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger, tower bottom reboiler, the hot fluid section of liquefaction heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The cold fluid section of the liquid outlet of cryogen gas-liquid separator, the hot fluid section of cooling heat exchanger, cooling heat exchanger is connected successively; The cold fluid section of cooling heat exchanger and the compression of azeotrope compressor one section are connected; This part Structure composing recycle circuit of azeotrope;

Hot fluid section, the dehydrogenation rectifying column charging aperture of the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger are connected successively; The overhead gas outlet of dehydrogenation rectifying column, the condensation segment of an overhead condensation evaporimeter, a tower overhead gas liquid/gas separator charging aperture are connected successively; The liquid outlet of a tower overhead gas liquid/gas separator and the phegma entrance of dehydrogenation rectifying column are connected, and the gas vent of a tower overhead gas liquid/gas separator, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, the cold fluid section of precool heat exchanger device are connected successively; At the bottom of the tower of dehydrogenation rectifying column, the charging aperture of liquid outlet and denitrogenation rectifying column is connected; The overhead gas outlet of denitrogenation rectifying column, the condensation segment of No. two overhead condensation evaporimeters, the charging aperture of No. two tower overhead gas liquid/gas separators are connected successively; The liquid outlet of No. two tower overhead gas liquid/gas separators and the phegma entrance of denitrogenation rectifying column are connected, and the gas vent of No. two tower overhead gas liquid/gas separators, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, the cold fluid section of precool heat exchanger device are connected successively; At the bottom of the tower of denitrogenation rectifying column, the hot fluid section of liquid outlet and liquefaction heat exchanger is connected; The liquefaction of this part Structure composing high methane gas and split circuit;

Compression one section, No. two intercoolers, the compression two sections of nitrogen compressor, No. two aftercoolers, the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, the hot fluid section of liquefaction heat exchanger, the liquid nitrogen of nitrogen compressor are crossed cold heat exchanger super cooled sect and are connected successively; The super cooled sect that liquid nitrogen crosses cold heat exchanger is connected with the evaporator section of No. two overhead condensation evaporimeters, an overhead condensation evaporator evaporation section respectively; The evaporator section of No. two overhead condensation evaporimeters, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, nitrogen compressor compress one section and connect successively; The evaporator section of an overhead condensation evaporimeter, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section nitrogen compressor of cooling heat exchanger compress one section and connect successively; This part Structure composing nitrogen refrigerant cycle circuit.

Precool heat exchanger device of the present invention, cooling heat exchanger, liquefaction heat exchanger are plate-fin heat exchanger.

Adopt said apparatus from high methane gas, produce a method for liquefied natural gas and rich hydrogen production, comprise azeotrope cyclic process, high methane gas liquefaction and separation process, nitrogen refrigerant cycle process;

Azeotrope cyclic process: mixed working fluid enters azeotrope suction port of compressor, compressed one section be compressed to 0.8 ~ 1.3MPa after enter an intercooler and be cooled to 30 ~ 50 DEG C, then enter middle knockout drum and carry out gas-liquid separation; The isolated gas of middle knockout drum continues the compression two sections of entrances entering azeotrope compressor, enter an aftercooler 3 after being compressed to 2.0 ~ 4.0MPa through two sections again and be cooled to 30 ~ 50 DEG C, enter precool heat exchanger device again and participate in heat exchange, be cooled to 5 ~ 12 DEG C; Mixed working fluid after precooling enters in cryogen gas-liquid separator and carries out gas-liquid separation, the gas that cryogen gas-liquid separator separates goes out enters cooling heat exchanger and participates in heat exchange, liquefaction heat exchanger is entered after being chilled to-60 ~-90 DEG C in advance, be cooled to-115 ~-135 DEG C, enter tower bottom reboiler again, liquefaction heat exchanger is returned after being cooled to-125 ~-145 DEG C as the thermal source of denitrogenation rectifying column, be cooled to-155 ~-165 DEG C, liquefaction heat exchanger is returned, for it provides cold by re-heat to-65 ~-95 DEG C after throttling to 0.23 again ~ 0.43MPa; The liquid that cryogen gas-liquid separator separates goes out enters cooling heat exchanger section and participates in heat exchange, be cooled to-60 ~-90 DEG C wherein, the mixed working fluid stream stock returned with liquefaction heat exchanger after throttling to 0.2 ~ 0.4MPa converges merging and oppositely enters cooling heat exchanger, for it provides cold, the compression one section of inlet compression entering azeotrope compressor behind re-heat to 5 ~ 12 DEG C again forms azeotrope circulation;

High methane gas liquefaction and separation process: the high methane gas after purification enters cooling heat exchanger and is cooled to-60 ~-90 DEG C after precool heat exchanger device is chilled to 5 ~ 12 DEG C in advance, enter again after liquefaction heat exchanger is cooled to-135 ~-155 DEG C and enter the rectifying of dehydrogenation rectifying column, enter a tower overhead gas liquid/gas separator after dehydrogenation rectifying tower top gaseous body is cooled to-165 ~-180 DEG C in an overhead condensation evaporimeter and carry out gas-liquid separation, the liquid that tower overhead gas liquid/gas separator is separated returns dehydrogenation rectifying column as phegma provides cold for it, an isolated hydrogen-rich gas in tower overhead gas liquid/gas separator top enters liquid nitrogen subcooler successively, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich hydrogen production, the still liquid of dehydrogenation rectifying column sends into the rectifying of denitrogenation rectifying column after throttling, enter No. two tower overhead gas liquid/gas separators after denitrogenation rectifying column top gas is cooled to-165 ~-180 DEG C in No. two overhead condensation evaporimeters and carry out gas-liquid separation, No. two isolated liquid of tower overhead gas liquid/gas separator return denitrogenation rectifying column as phegma provides cold for it, No. two isolated gases of tower overhead gas liquid/gas separator enter liquid nitrogen successively and cross cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich nitrogen product, distillate at the bottom of the tower of denitrogenation rectifying column is-135 ~-145 DEG C, is rich in the liquefied natural gas of methane, returns liquefaction heat exchanger and is chilled to-160 ~-170 DEG C, sends into LNG storage tank and store after throttling,

Nitrogen refrigerant cycle process: nitrogen through nitrogen compressor compress one section be pressurized to 1.0 ~ 1.8MPa after be cooled to 30 ~ 50 DEG C through No. two intercoolers, enter nitrogen compressor again to compress two sections and be pressurized to 3.0 ~ 4.0MPa, 30 ~ 50 DEG C are cooled to successively through No. two aftercoolers, after precool heat exchanger device is cooled to 5 ~ 12 DEG C, enter cooling heat exchanger more successively and be cooled to-60 ~-90 DEG C, liquefaction heat exchanger is cooled to-150 ~-165 DEG C, cross in cold heat exchanger to be crossed at liquid nitrogen again and be chilled to-165 ~-180 DEG C, finally cross cold liquid nitrogen to enter No. two overhead condensation evaporimeters and overhead condensation evaporimeter respectively for overhead gas cooling cold is provided, low temperature nitrogen after No. two overhead condensation evaporimeters and an overhead condensation evaporimeter liquid nitrogen vaporization crosses cold heat exchanger through liquid nitrogen successively, liquefaction heat exchanger, cooling heat exchanger reclaim cold, enter nitrogen compressor behind re-heat to 7 ~ 15 DEG C and compress one section of supercharging again, form nitrogen refrigerant cycle.

The present invention provides cold using the chilled brine of 5 ~ 9 DEG C as the cold stock of precool heat exchanger device for it, is gone out precool heat exchanger device by re-heat to 7 ~ 12 DEG C.

The present invention compared with prior art, have the following advantages and effect: traditional hybrid refrigeration associating liquid nitrogen refrigerating produces the technique of liquefied natural gas and rich hydrogen production from high methane gas, the low temperature nitrogen that the low temperature hydrogen rich gas that rectifying column produces, rich nitrogen and condenser produce provides cold in two ways: one returns main heat exchanger for all hot-fluid stocks to provide cold, and a kind of is for crossing the liquefied natural gas distillated at the bottom of cold rectifying column.And in the present invention, the low temperature nitrogen of the low temperature hydrogen-rich gas that rectifying column produces, nitrogen-rich gas and condenser external liquid nitrogen vaporization was used for the cold liquid nitrogen from main heat exchanger, be different from traditional supercooled liquid natural gas, due to cold flow stock and hot-fluid stock physical property closer to, the cold fluid of whole heat exchanger process and the heat exchange curve of hot fluid more mate, therefore heat exchanger cold-end temperature difference is less, and therefore heat exchange efficiency is higher, energy consumption is lower.

Accompanying drawing explanation

Fig. 1 is the structural representation of the embodiment of the present invention.

Detailed description of the invention

Below in conjunction with accompanying drawing, also by embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.

See Fig. 1, from high methane gas, produce the device of liquefied natural gas and rich hydrogen production, comprise azeotrope compressor refrigeration system, chilldown system, liquefaction cold box system, nitrogen compressor system, and the connecting line between each system and equipment thereof.From high methane gas, produce the method for liquefied natural gas and rich hydrogen production, comprise azeotrope cyclic process, high methane gas liquefaction and separation process, nitrogen refrigerant cycle process.

Azeotrope compressor refrigeration system comprises a motor and drives or knockout drum 4 in the middle of steam-powered azeotrope compressor 1, intercooler 2, aftercooler 3.Azeotrope compressor 1 has compression one section and compression two sections.

Chilldown system comprises a precool heat exchanger device 8, cryogen gas-liquid separator 11.

Liquefaction cold box system comprises a cooling heat exchanger 9, liquefaction heat exchanger 10, liquid nitrogen and crosses cold heat exchanger 16, denitrogenation rectifying column 14, dehydrogenation rectifying column 17; The tower top of dehydrogenation rectifying column 17 is provided with an overhead condensation evaporimeter 19 and a tower overhead gas liquid/gas separator 18; Be provided with tower bottom reboiler 15 at the bottom of the tower of denitrogenation rectifying column 14, tower top is provided with No. two overhead condensation evaporimeters 12 and No. two tower overhead gas liquid/gas separators 13.

Nitrogen compressor refrigeration system comprises a motor and drives or steam-powered nitrogen compressor 5, No. two intercooler 6, No. two aftercooler 7.Nitrogen compressor 5 has compression one section and compression two sections.

Azeotrope recycle circuit: compression one section, intercooler 2, middle knockout drum 4, the compression two sections of azeotrope compressor 1, aftercooler 3, the hot fluid section of precool heat exchanger device 8, a compound import for cryogen gas-liquid separator 11 of azeotrope compressor 1 are connected successively.The hot fluid section of the gas vent of cryogen gas-liquid separator 11, the hot fluid section of cooling heat exchanger 9, liquefaction heat exchanger 10, tower bottom reboiler 15, the hot fluid section of liquefaction heat exchanger 10, the cold fluid section of liquefaction heat exchanger 10, the cold fluid section of cooling heat exchanger 9 are connected successively.The cold fluid section of the liquid outlet of cryogen gas-liquid separator 11, the hot fluid section of cooling heat exchanger 9, cooling heat exchanger 9 is connected successively.The cold fluid section of cooling heat exchanger 9 and the compression of azeotrope compressor 1 one section are connected.

Azeotrope cyclic process: the mixed working fluid be made up of C1 ~ C5 and nitrogen enters azeotrope compressor 1 entrance through rational proportion, compressed one section be compressed to 0.8 ~ 1.3MPa after enter an intercooler 2 and be cooled to 30 ~ 50 DEG C, then enter middle knockout drum 4 and carry out gas-liquid separation, the isolated gas in middle knockout drum 4 top continues the compression two sections of entrances entering azeotrope compressor 1, enter an aftercooler 3 after being compressed to 2.0 ~ 4.0MPa through two sections again and be cooled to 30 ~ 50 DEG C, enter precool heat exchanger device 8 hot fluid section again and participate in heat exchange, be cooled to 5 ~ 12 DEG C, mixed working fluid after precooling enters in cryogen gas-liquid separator 11 and carries out gas-liquid separation, the hot fluid section that the gas that cryogen gas-liquid separator 11 top gas exports out enters the cooling heat exchanger 9 of liquefaction ice chest participates in heat exchange, entered the hot fluid section of liquefaction heat exchanger 10 after being chilled to-60 ~-90 DEG C in advance, be cooled to-115 ~-135 DEG C, enter tower bottom reboiler 15 again, the hot fluid section of liquefaction heat exchanger 10 is returned after being cooled to-125 ~-145 DEG C as the thermal source of denitrogenation rectifying column 14, be cooled to-155 ~-165 DEG C, the cold fluid section of liquefaction heat exchanger 10 is returned after throttling to 0.23 again ~ 0.43MPa, for it provides cold by re-heat to-65 ~-95 DEG C.Liquid outlet bottom cryogen gas-liquid separator 11 liquid out enters the cooling heat exchanger 9 of liquefaction ice chest hot fluid section as liquid phase cryogen participates in heat exchange, be cooled to-60 ~-90 DEG C wherein, the mixed working fluid stream stock returned with liquefaction heat exchanger 10 after throttling to 0.2 ~ 0.4MPa converges the cold fluid section that merging oppositely enters cooling heat exchanger 9, for it provides cold, the compression one section of inlet compression entering azeotrope compressor 1 behind re-heat to 5 ~ 12 DEG C again forms azeotrope circulation.

High methane gas liquefaction and split circuit: hot fluid section, dehydrogenation rectifying column 17 charging aperture of the hot fluid section of precool heat exchanger device 8, the hot fluid section of cooling heat exchanger 9, liquefaction heat exchanger 10 are connected successively.The overhead gas outlet of dehydrogenation rectifying column 17, the condensation segment of an overhead condensation evaporimeter 19, tower overhead gas liquid/gas separator 18 charging aperture are connected successively.The liquid outlet of a tower overhead gas liquid/gas separator 18 and the phegma entrance of dehydrogenation rectifying column 17 are connected, and the gas vent of a tower overhead gas liquid/gas separator 18, liquid nitrogen cross the super cooled sect of cold heat exchanger 16, the cold fluid section of liquefaction heat exchanger 10, the cold fluid section of cooling heat exchanger 9, the cold fluid section of precool heat exchanger device 8 are connected successively.At the bottom of the tower of dehydrogenation rectifying column 17, the charging aperture of liquid outlet and denitrogenation rectifying column 14 is connected.The overhead gas outlet of denitrogenation rectifying column 14, the condensation segment of No. two overhead condensation evaporimeters 12, the charging aperture of No. two tower overhead gas liquid/gas separators 13 are connected successively.The liquid outlet of No. two tower overhead gas liquid/gas separators and the phegma entrance of denitrogenation rectifying column 14 are connected, and the gas vent of No. two tower overhead gas liquid/gas separators 13, liquid nitrogen cross the super cooled sect of cold heat exchanger 16, the cold fluid section of liquefaction heat exchanger 10, the cold fluid section of cooling heat exchanger 9, the cold fluid section of precool heat exchanger device 8 are connected successively; At the bottom of the tower of denitrogenation rectifying column 14, the hot fluid section of liquid outlet and liquefaction heat exchanger 10 is connected.

High methane gas liquefaction and separation process: the cooling heat exchanger 9 that the high methane gas after purification enters liquefaction ice chest after precool heat exchanger device 8 is chilled to 5 ~ 12 DEG C is in advance cooled to-60 ~-90 DEG C, enter again after liquefaction heat exchanger 10 is cooled to-135 ~-155 DEG C and enter dehydrogenation rectifying column 17 rectifying, dehydrogenation rectifying column 17 overhead gas is entered a tower overhead gas liquid/gas separator 18 after cooled with liquid nitrogen extremely-165 ~-180 DEG C and is carried out gas-liquid separation in an overhead condensation evaporimeter 19, a tower overhead gas liquid/gas separator 18 liquid out returns as phegma as dehydrogenation rectifying column 17 provides cold from the phegma entrance at dehydrogenation rectifying column 17 top, a tower overhead gas liquid/gas separator 18 top isolated hydrogen content 85%(volume) more than hydrogen-rich gas enter liquid nitrogen subcooler 16 successively, liquefaction heat exchanger 10, cooling heat exchanger 9, precool heat exchanger device 8 provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich hydrogen production.Dehydrogenation rectifying column 17 still liquid sends into denitrogenation rectifying column 14 rectifying after throttling, denitrogenation rectifying column 14 top gas is entered No. two tower overhead gas liquid/gas separators 13 after cooled with liquid nitrogen extremely-165 ~-180 DEG C and is carried out gas-liquid separation in No. two overhead condensation evaporimeters 12, No. two tower overhead gas liquid/gas separators 13 liquid out returns as phegma as denitrogenation rectifying column 14 provides cold from the phegma entrance at denitrogenation rectifying column 14 top, the isolated nitrogen-rich gas in No. two tower overhead gas liquid/gas separator 13 tops enters liquid nitrogen successively and crosses cold heat exchanger 16, liquefaction heat exchanger 10, cooling heat exchanger 9, precool heat exchanger device 8 provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich nitrogen product.Distillate at the bottom of the tower of denitrogenation rectifying column 14 is-135 ~-145 DEG C, methane content >=98%(volume) liquefied natural gas, return liquefaction heat exchanger 10 and be chilled to-160 ~-170 DEG C, send into after throttling LNG storage tank store.

Nitrogen refrigerant cycle circuit: compression one section, No. two intercoolers 6, the compression two sections of nitrogen compressor 5, No. two aftercoolers 7, the hot fluid section of precool heat exchanger device 8, the hot fluid section of cooling heat exchanger 9, the hot fluid section of liquefaction heat exchanger 10, the liquid nitrogen of nitrogen compressor 5 are crossed cold heat exchanger 16 super cooled sect and connected successively.The super cooled sect that liquid nitrogen crosses cold heat exchanger 16 is connected with the evaporator section of No. two overhead condensation evaporimeters 12, overhead condensation evaporimeter 19 evaporator section respectively.The evaporator section of No. two overhead condensation evaporimeters 12, liquid nitrogen cross the super cooled sect of cold heat exchanger 16, the cold fluid section of liquefaction heat exchanger 10, the cold fluid section of cooling heat exchanger 9, nitrogen compressor 5 compress one section and connect successively.The evaporator section of an overhead condensation evaporimeter 19, liquid nitrogen cross the super cooled sect of cold heat exchanger 16, the cold fluid section of liquefaction heat exchanger 10, the cold fluid section nitrogen compressor 5 of cooling heat exchanger 9 compress one section and connect successively.

Nitrogen refrigerant cycle process: nitrogen through nitrogen compressor 5 compress one section be pressurized to 1.0 ~ 1.8MPa after be cooled to 30 ~ 50 DEG C through No. two intercoolers 6, enter nitrogen compressor 5 again to compress two sections and be pressurized to 3.0 ~ 4.0MPa, 30 ~ 50 DEG C are cooled to successively through No. two aftercoolers 7, after precool heat exchanger device 8 is cooled to 5 ~ 12 DEG C, the cooling heat exchanger 9 entering liquefaction ice chest is more successively cooled to-60 ~-90 DEG C, liquefaction heat exchanger 10 is cooled to-150 ~-165 DEG C, cross in cold heat exchanger 16 by the low temperature hydrogen-rich gas backflowed at liquid nitrogen again, the rich nitrogen of low temperature and low temperature nitrogen are crossed and are chilled to-165 ~-180 DEG C, finally cross No. two overhead condensation evaporimeters 12 that cold liquid nitrogen enters denitrogenation rectifying column 14 respectively, an overhead condensation evaporimeter 19 of dehydrogenation rectifying column 17 provides cold for overhead gas cools.Low temperature nitrogen after No. two overhead condensation evaporimeters 12 and overhead condensation evaporimeter 19 liquid nitrogen vaporization crosses cold heat exchanger 16 through liquid nitrogen successively, liquefaction heat exchanger 10, cooling heat exchanger 9 reclaim cold, enter nitrogen compressor 5 behind re-heat to 7 ~ 15 DEG C and compress one section of supercharging again, form nitrogen refrigerant cycle.

Chilled brine pipeline: the chilled brine of 5 ~ 9 DEG C from lithium bromide precooling unit provides cold as the cold stock of precool heat exchanger device 8 for it, is gone out precool heat exchanger device 8 by re-heat to 7 ~ 12 DEG C.

Precool heat exchanger device 8, cooling heat exchanger 9, liquefaction heat exchanger 10 are plate-fin heat exchanger.

Fluid in the hot fluid section of above-described each heat exchanger receives cold, and temperature reduces; Fluid in cold fluid section provides cold, and temperature raises, and this concept is the common practise of this area.

In addition, it should be noted that, the specific embodiment described in this description, the shape, institute's title of being named etc. of its parts and components can be different, and the above content described in this description is only to structure example of the present invention explanation.

Claims (4)

1. from high methane gas, produce a device for liquefied natural gas and rich hydrogen production, it is characterized in that: comprise azeotrope compressor refrigeration system, chilldown system, liquefaction cold box system, nitrogen compressor system; Described azeotrope compressor refrigeration system comprises azeotrope compressor, an intercooler, aftercooler, a middle knockout drum; Azeotrope compressor has compression one section and compression two sections; Described chilldown system comprises precool heat exchanger device, cryogen gas-liquid separator; Described liquefaction cold box system comprises cooling heat exchanger, liquefaction heat exchanger, liquid nitrogen cross cold heat exchanger, denitrogenation rectifying column, dehydrogenation rectifying column; The tower top of dehydrogenation rectifying column is provided with an overhead condensation evaporimeter and a tower overhead gas liquid/gas separator; Be provided with tower bottom reboiler at the bottom of the tower of denitrogenation rectifying column, tower top is provided with No. two overhead condensation evaporimeters and No. two tower overhead gas liquid/gas separators; Described nitrogen compressor refrigeration system comprises nitrogen compressor, No. two intercoolers, No. two aftercoolers;
Compression one section, intercooler, middle knockout drum, the compression two sections of azeotrope compressor, aftercooler, the hot fluid section of precool heat exchanger device, a compound import for cryogen gas-liquid separator of azeotrope compressor are connected successively; The hot fluid section of the gas vent of cryogen gas-liquid separator, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger, tower bottom reboiler, the hot fluid section of liquefaction heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The cold fluid section of the liquid outlet of cryogen gas-liquid separator, the hot fluid section of cooling heat exchanger, cooling heat exchanger is connected successively; The cold fluid section of cooling heat exchanger and the compression of azeotrope compressor one section are connected;
Hot fluid section, the dehydrogenation rectifying column charging aperture of the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger are connected successively; The overhead gas outlet of dehydrogenation rectifying column, the condensation segment of an overhead condensation evaporimeter, a tower overhead gas liquid/gas separator charging aperture are connected successively; The liquid outlet of a tower overhead gas liquid/gas separator and the phegma entrance of dehydrogenation rectifying column are connected, and the gas vent of a tower overhead gas liquid/gas separator, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, the cold fluid section of precool heat exchanger device are connected successively; At the bottom of the tower of dehydrogenation rectifying column, the charging aperture of liquid outlet and denitrogenation rectifying column is connected; The overhead gas outlet of denitrogenation rectifying column, the condensation segment of No. two overhead condensation evaporimeters, the charging aperture of No. two tower overhead gas liquid/gas separators are connected successively; The liquid outlet of No. two tower overhead gas liquid/gas separators and the phegma entrance of denitrogenation rectifying column are connected, and the gas vent of No. two tower overhead gas liquid/gas separators, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, the cold fluid section of precool heat exchanger device are connected successively; At the bottom of the tower of denitrogenation rectifying column, the hot fluid section of liquid outlet and liquefaction heat exchanger is connected;
Compression one section, No. two intercoolers, the compression two sections of nitrogen compressor, No. two aftercoolers, the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, the hot fluid section of liquefaction heat exchanger, the liquid nitrogen of nitrogen compressor are crossed cold heat exchanger super cooled sect and are connected successively; The super cooled sect that liquid nitrogen crosses cold heat exchanger is connected with the evaporator section of No. two overhead condensation evaporimeters, an overhead condensation evaporator evaporation section respectively; The evaporator section of No. two overhead condensation evaporimeters, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section of cooling heat exchanger, nitrogen compressor compress one section and connect successively; The evaporator section of an overhead condensation evaporimeter, liquid nitrogen cross the super cooled sect of cold heat exchanger, the cold fluid section of liquefaction heat exchanger, the cold fluid section nitrogen compressor of cooling heat exchanger compress one section and connect successively.
2. the device producing liquefied natural gas and rich hydrogen production from high methane gas according to claim 1, is characterized in that: described precool heat exchanger device, cooling heat exchanger, liquefaction heat exchanger are plate-fin heat exchanger.
3. adopt the device described in claim 1 or 2 from high methane gas, produce a method for liquefied natural gas and rich hydrogen production, it is characterized in that: comprise azeotrope cyclic process, high methane gas liquefaction and separation process, nitrogen refrigerant cycle process;
Azeotrope cyclic process: mixed working fluid enters azeotrope suction port of compressor, compressed one section be compressed to 0.8 ~ 1.3MPa after enter an intercooler and be cooled to 30 ~ 50 DEG C, then enter middle knockout drum and carry out gas-liquid separation; The isolated gas of middle knockout drum continues the compression two sections of entrances entering azeotrope compressor, enter an aftercooler 3 after being compressed to 2.0 ~ 4.0MPa through two sections again and be cooled to 30 ~ 50 DEG C, enter precool heat exchanger device again and participate in heat exchange, be cooled to 5 ~ 12 DEG C; Mixed working fluid after precooling enters in cryogen gas-liquid separator and carries out gas-liquid separation, the gas that cryogen gas-liquid separator separates goes out enters cooling heat exchanger and participates in heat exchange, liquefaction heat exchanger is entered after being chilled to-60 ~-90 DEG C in advance, be cooled to-115 ~-135 DEG C, enter tower bottom reboiler again, liquefaction heat exchanger is returned after being cooled to-125 ~-145 DEG C as the thermal source of denitrogenation rectifying column, be cooled to-155 ~-165 DEG C, liquefaction heat exchanger is returned, for it provides cold by re-heat to-65 ~-95 DEG C after throttling to 0.23 again ~ 0.43MPa; The liquid that cryogen gas-liquid separator separates goes out enters cooling heat exchanger section and participates in heat exchange, be cooled to-60 ~-90 DEG C wherein, the mixed working fluid stream stock returned with liquefaction heat exchanger after throttling to 0.2 ~ 0.4MPa converges merging and oppositely enters cooling heat exchanger, for it provides cold, the compression one section of inlet compression entering azeotrope compressor behind re-heat to 5 ~ 12 DEG C again forms azeotrope circulation;
High methane gas liquefaction and separation process: the high methane gas after purification enters cooling heat exchanger and is cooled to-60 ~-90 DEG C after precool heat exchanger device is chilled to 5 ~ 12 DEG C in advance, enter again after liquefaction heat exchanger is cooled to-135 ~-155 DEG C and enter the rectifying of dehydrogenation rectifying column, enter a tower overhead gas liquid/gas separator after dehydrogenation rectifying tower top gaseous body is cooled to-165 ~-180 DEG C in an overhead condensation evaporimeter and carry out gas-liquid separation, the liquid that tower overhead gas liquid/gas separator is separated returns dehydrogenation rectifying column as phegma provides cold for it, an isolated hydrogen-rich gas in tower overhead gas liquid/gas separator top enters liquid nitrogen subcooler successively, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich hydrogen production, the still liquid of dehydrogenation rectifying column sends into the rectifying of denitrogenation rectifying column after throttling, enter No. two tower overhead gas liquid/gas separators after denitrogenation rectifying column top gas is cooled to-165 ~-180 DEG C in No. two overhead condensation evaporimeters and carry out gas-liquid separation, No. two isolated liquid of tower overhead gas liquid/gas separator return denitrogenation rectifying column as phegma provides cold for it, No. two isolated gases of tower overhead gas liquid/gas separator enter liquid nitrogen successively and cross cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device provides cold as the cold stock that backflows for heat exchanger, final re-heat to 30 ~ 40 are DEG C as rich nitrogen product, distillate at the bottom of the tower of denitrogenation rectifying column is-135 ~-145 DEG C, is rich in the liquefied natural gas of methane, returns liquefaction heat exchanger and is chilled to-160 ~-170 DEG C, sends into LNG storage tank and store after throttling,
Nitrogen refrigerant cycle process: nitrogen through nitrogen compressor compress one section be pressurized to 1.0 ~ 1.8MPa after be cooled to 30 ~ 50 DEG C through No. two intercoolers, enter nitrogen compressor again to compress two sections and be pressurized to 3.0 ~ 4.0MPa, 30 ~ 50 DEG C are cooled to successively through No. two aftercoolers, after precool heat exchanger device is cooled to 5 ~ 12 DEG C, enter cooling heat exchanger more successively and be cooled to-60 ~-90 DEG C, liquefaction heat exchanger is cooled to-150 ~-165 DEG C, cross in cold heat exchanger to be crossed at liquid nitrogen again and be chilled to-165 ~-180 DEG C, finally cross cold liquid nitrogen to enter No. two overhead condensation evaporimeters and overhead condensation evaporimeter respectively for overhead gas cooling cold is provided, low temperature nitrogen after No. two overhead condensation evaporimeters and an overhead condensation evaporimeter liquid nitrogen vaporization crosses cold heat exchanger through liquid nitrogen successively, liquefaction heat exchanger, cooling heat exchanger reclaim cold, enter nitrogen compressor behind re-heat to 7 ~ 15 DEG C and compress one section of supercharging again, form nitrogen refrigerant cycle.
4. the method producing liquefied natural gas and rich hydrogen production from high methane gas according to claim 3, is characterized in that: provide cold using the chilled brine of 5 ~ 9 DEG C as the cold stock of precool heat exchanger device for it, gone out precool heat exchanger device by re-heat to 7 ~ 12 DEG C.
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