CN103697659A - Device and method for manufacturing liquefied natural gas and hydrogen-rich products out of high methane gas - Google Patents
Device and method for manufacturing liquefied natural gas and hydrogen-rich products out of high methane gas Download PDFInfo
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes 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
- F25J3/0204—Processes 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
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes 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
- F25J3/0228—Processes 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
- F25J3/0233—Processes 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
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes 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
- F25J3/0228—Processes 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
- F25J3/0252—Processes 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
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes 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
- F25J3/0228—Processes 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
- F25J3/0257—Processes 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
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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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
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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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/04—Recovery of liquid products
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/12—External refrigeration with liquid vaporising loop
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/18—External refrigeration with incorporated cascade loop
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
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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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/34—Details about subcooling of liquids
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Abstract
The invention relates to a device and method for manufacturing liquefied natural gas and hydrogen-rich products out of high methane gas. The device comprises a mixed refrigerant compressor refrigerating system, a precooling system, a liquefying cold box system and a nitrogen compressor system. The method comprises a mixed refrigerant cycle process, a high methane gas liquification and separation process and a nitrogen refrigerant cycle process. Low-temperature hydrogen-rich gas and nitrogen-rich gas generated by rectifying towers and low-temperature nitrogen evaporated out of liquid nitrogen on the outer portion of a condenser are used for undercooling the liquid nitrogen before the liquid nitrogen enters a condensing evaporator, thereby being different from traditional undercooling of the liquefied natural gas; heat exchange curves of cold fluid and hot fluid in the whole heat exchanger process are better matched, the temperature difference of heat exchanger cold ends is smaller, heat exchange efficiency is higher, and energy consumption is lower.
Description
Technical field
The present invention relates to a kind of device and method of 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 become methane, the methane volume fraction that the synthesis gas of gained obtains after the purification after naphthalene, desulfurization are washed in water washing de-oiling is again more than 40～50%, is separately rich in hydrogen and nitrogen.High methane gas is prepared LNG and rich hydrogen production through low-temperature liquefaction, cryogenic rectification again.The coke-stove gas that is the richest in alkanisation through purifying, liquefaction is separated prepares liquefied natural gas and not only can alleviate the problem of domestic natural gas shortage, and can promote technological progress and the industry development of coking and energy industry, development coke-stove gas LNG project processed can produce obvious economic benefit, environmental benefit and social benefit, coke-stove gas is recycled to industry significant.
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 is produced 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: a kind of is to return to main heat exchanger to provide cold for all hot-fluid thighs, and a kind of is the liquefied natural gas distillating at the bottom of cold rectifying column for crossing.
Application number is 201210065876.5, name is called from high methane gas dehydrogenation nitrogen and produce the technique of liquefied natural gas and the Chinese patent of device, application number is 201110291609.5, name is called from high methane gas dehydrogenation gas, nitrogen, carbon monoxide and produce the Chinese patent of the technique of liquefied natural gas, these prior aries are Shortcomings still at aspects such as the liquefaction of refrigeration, high methane gas and separating effects, specific energy consumption is higher, and hydrogen-rich gas is produced to deficiency, 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 of producing liquefied natural gas and rich hydrogen production from high methane gas that cost is low is provided.
The present invention addresses the above problem adopted technical scheme: a kind of device of producing liquefied natural gas and rich hydrogen production from high methane gas, comprises azeotrope compressor refrigeration system, chilldown system, liquefaction ice chest system, nitrogen compressor system; Described azeotrope compressor refrigeration system comprises azeotrope compressor, intercooler, aftercooler, middle knockout drum; Azeotrope compressor has one section of compression and compresses two sections; Described chilldown system comprises precool heat exchanger device, cryogen gas-liquid separator; Described liquefaction ice chest system comprises that 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; At the bottom of the tower of denitrogenation rectifying column, be provided with tower bottom reboiler, 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;
Two sections, No. one aftercooler of compression of one section, No. one intercooler of compression of azeotrope compressor, middle knockout drum, azeotrope compressor, the hot fluid section of precool heat exchanger device, the compound import of cryogen gas-liquid separator are connected successively; The hot fluid section of the hot fluid section of the hot fluid section of the gas vent of cryogen gas-liquid separator, cooling heat exchanger, liquefaction heat exchanger, tower bottom reboiler, liquefaction heat exchanger, the liquefaction cold fluid section of heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The hot fluid section of the liquid outlet of cryogen gas-liquid separator, cooling heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The cold fluid section of cooling heat exchanger and one section of connection of the compression of azeotrope compressor; This part structure has formed the 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 phegma entrance of the liquid outlet of a tower overhead gas liquid/gas separator and dehydrogenation rectifying column is connected, and the gas vent of a tower overhead gas liquid/gas separator, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of the cold fluid section of cooling heat exchanger, precool heat exchanger device of cold heat exchanger and 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 phegma entrance of the liquid outlet of No. two tower overhead gas liquid/gas separators and denitrogenation rectifying column is connected, and the gas vent of No. two tower overhead gas liquid/gas separators, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of the cold fluid section of cooling heat exchanger, precool heat exchanger device of cold heat exchanger and connected successively; At the bottom of the tower of denitrogenation rectifying column, liquid outlet is connected with the hot fluid section of liquefaction heat exchanger; This part structure has formed high methane gas liquefaction and split circuit;
Hot fluid section, the liquid nitrogen of one section, No. two intercoolers of compression of nitrogen compressor, two sections, No. two aftercoolers of compression of nitrogen compressor, the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger are crossed cold heat exchanger super cooled sect and are connected successively; Liquid nitrogen is crossed the super cooled sect of cold heat exchanger and 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 are crossed one section of connection successively of super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of cooling heat exchanger, nitrogen compressor compression of cold heat exchanger; The evaporator section of an overhead condensation evaporimeter, liquid nitrogen are crossed one section of connection successively of super cooled sect, the liquefaction cold fluid section of heat exchanger, the compression of the cold fluid section nitrogen compressor of cooling heat exchanger of cold heat exchanger; This part structure has formed 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, to 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 is compressed to and enters an intercooler after 0.8～1.3MPa and be cooled to 30～50 ℃, then in the middle of entering, knockout drum carries out gas-liquid separation; The isolated gas of middle knockout drum continues to enter two sections of entrances of compression of azeotrope compressor, after two sections are compressed to 2.0～4.0MPa, enter again an aftercooler 3 and be cooled to 30～50 ℃, enter again precool heat exchanger device and participate in heat exchange, be cooled to 5～12 ℃; Mixed working fluid after precooling enters and in cryogen gas-liquid separator, carries out gas-liquid separation, the gas that cryogen gas-liquid separator separates goes out enters cooling heat exchanger and participates in heat exchange, after being chilled in advance-60～-90 ℃, enter liquefaction heat exchanger, be cooled to-115～-135 ℃, enter again tower bottom reboiler, thermal source as denitrogenation rectifying column returns to liquefaction heat exchanger after being cooled to-125～-145 ℃, be cooled to-155～-165 ℃, after throttling to 0.23 again～0.43MPa, return to liquefaction heat exchanger, for it provides cold by extremely-65～-95 ℃ of re-heats; The liquid that cryogen gas-liquid separator separates goes out enters cooling heat exchanger section and participates in heat exchange, be cooled to therein-60～-90 ℃, the mixed working fluid stream strand returning with liquefaction heat exchanger after throttling to 0.2～0.4MPa converges merging and oppositely enters cooling heat exchanger, for it provides cold, the one section of entrance compression of compression that enters again azeotrope compressor behind re-heat to 5～12 ℃ 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 ℃ after precool heat exchanger device is chilled to 5～12 ℃ in advance, enter again after liquefaction heat exchanger is cooled to-135～-155 ℃ and enter the rectifying of dehydrogenation rectifying column, dehydrogenation rectifying tower top gaseous body enters a tower overhead gas liquid/gas separator be cooled to-165～-180 ℃ in an overhead condensation evaporimeter after and carries out gas-liquid separation, the liquid that tower overhead gas liquid/gas separator is separated returns to dehydrogenation rectifying column as phegma provides cold for it, No. one the 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 cold strand provides cold for heat exchanger as backflowing, the final rich hydrogen production of re-heat to 30～40 ℃ conduct, the still liquid of dehydrogenation rectifying column is sent into the rectifying of denitrogenation rectifying column after throttling, denitrogenation rectifying column top gas enters No. two tower overhead gas liquid/gas separators be cooled to-165～-180 ℃ in No. two overhead condensation evaporimeters after and carries out gas-liquid separation, No. two isolated liquid of tower overhead gas liquid/gas separator return to denitrogenation rectifying column as phegma provides cold for it, No. two isolated gases of tower overhead gas liquid/gas separator enter successively liquid nitrogen and cross cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device cold strand provides cold for heat exchanger as backflowing, the final rich nitrogen product of re-heat to 30～40 ℃ conduct, at the bottom of the tower of denitrogenation rectifying column, distillate is-135～-145 ℃, is rich in the liquefied natural gas of methane, returns to liquefaction heat exchanger and is chilled to-160～-170 ℃, sends into LNG storage tank stores after throttling,
Nitrogen refrigerant cycle process: nitrogen is pressurized to 1.0～1.8MPa through one section of nitrogen compressor compression and is cooled to 30～50 ℃ by No. two intercoolers, enter again two sections of nitrogen compressor compressions and be pressurized to 3.0～4.0MPa, through No. two aftercoolers, be cooled to 30～50 ℃ successively, precool heat exchanger device is cooled to after 5～12 ℃, enter successively again cooling heat exchanger and be cooled to-60～-90 ℃, liquefaction heat exchanger is cooled to-150～-165 ℃, at liquid nitrogen, cross in cold heat exchanger and crossed and be chilled to-165～-180 ℃ again, finally cross that cold liquid nitrogen enters respectively No. two overhead condensation evaporimeters and an overhead condensation evaporimeter provides cold for overhead gas is cooling, low temperature nitrogen after No. two overhead condensation evaporimeters and an overhead condensation evaporimeter liquid nitrogen vaporization is crossed cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger recovery cold through liquid nitrogen successively, behind re-heat to 7～15 ℃, enter one section of supercharging again of nitrogen compressor compression, form nitrogen refrigerant cycle.
The chilled brine of 5～9 ℃ is take in the present invention strand provides cold as it as the cold of precool heat exchanger device, by re-heat to 7～12 ℃, is gone out precool heat exchanger device.
The present invention compared with prior art, have the following advantages and effect: traditional hybrid refrigeration associating liquid nitrogen refrigerating is produced 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: a kind of is to return to main heat exchanger to provide cold for all hot-fluid thighs, and a kind of is the liquefied natural gas distillating at the bottom of cold rectifying column for crossing.And in the present invention, the low temperature nitrogen of the outside liquid nitrogen vaporization of the low temperature hydrogen-rich gas that rectifying column produces, nitrogen-rich gas and condenser was used for the cold liquid nitrogen from main heat exchanger, be different from traditional supercooled liquid natural gas, because the physical property of cold flow thigh and hot-fluid thigh is more approaching, the heat exchange curve of the cold fluid of whole heat exchanger process and hot fluid more mates, therefore heat exchanger cold-end temperature difference is less, so 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.
The specific embodiment
Below in conjunction with accompanying drawing and 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.
Referring to 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 ice chest 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 that motor drives or steam-powered azeotrope compressor 1, intercooler 2, aftercooler 3, knockout drum 4 in the middle of.Azeotrope compressor 1 has one section of compression and compresses two sections.
Chilldown system comprises a precool heat exchanger device 8, a cryogen gas-liquid separator 11.
Liquefaction ice chest system comprises that a cooling heat exchanger 9, liquefaction heat exchanger 10, a liquid nitrogen cross 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; At the bottom of the tower of denitrogenation rectifying column 14, be provided with tower bottom reboiler 15, 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 that motor drives or steam-powered nitrogen compressor 5, No. two intercooler 6, No. two aftercoolers 7.Nitrogen compressor 5 has one section of compression and compresses two sections.
Azeotrope recycle circuit: one section, No. one intercooler 2 of compression of azeotrope compressor 1, middle knockout drum 4, two sections, No. one aftercooler 3 of compression of azeotrope compressor 1, the hot fluid section of precool heat exchanger device 8, the compound import of cryogen gas-liquid separator 11 are connected successively.The hot fluid section of the hot fluid section of the gas vent of cryogen gas-liquid separator 11, cooling heat exchanger 9, liquefaction heat exchanger 10, tower bottom reboiler 15, the hot fluid section of liquefaction heat exchanger 10, the liquefaction cold fluid section of heat exchanger 10, the cold fluid section of cooling heat exchanger 9 are connected successively.The hot fluid section of the liquid outlet of cryogen gas-liquid separator 11, cooling heat exchanger 9, the cold fluid section of cooling heat exchanger 9 are connected successively.The cold fluid section of cooling heat exchanger 9 and one section of connection of the compression of azeotrope compressor 1.
Azeotrope cyclic process: the mixed working fluid being comprised of C1～C5 and nitrogen enters azeotrope compressor 1 entrance through rational proportion, compressed one section is compressed to and enters an intercooler 2 after 0.8～1.3MPa and be cooled to 30～50 ℃, then in the middle of entering, knockout drum 4 carries out gas-liquid separation, the middle knockout drum 4 isolated gases in top continue to enter two sections of entrances of compression of azeotrope compressor 1, after two sections are compressed to 2.0～4.0MPa, enter again an aftercooler 3 and be cooled to 30～50 ℃, enter again precool heat exchanger device 8 hot fluid sections and participate in heat exchange, be cooled to 5～12 ℃, mixed working fluid after precooling enters and in cryogen gas-liquid separator 11, carries out gas-liquid separation, the hot fluid section that the gas that cryogen gas-liquid separator 11 top gas export out enters the cooling heat exchanger 9 of liquefaction ice chest participates in heat exchange, be chilled in advance the hot fluid section that enters liquefaction heat exchanger 10 after-60～-90 ℃, be cooled to-115～-135 ℃, enter again tower bottom reboiler 15, thermal source as denitrogenation rectifying column 14 is cooled to the hot fluid section of returning to liquefaction heat exchanger 10 after-125～-145 ℃, be cooled to-155～-165 ℃, after throttling to 0.23 again～0.43MPa, return to the cold fluid section of liquefaction heat exchanger 10, for it provides cold by extremely-65～-95 ℃ of re-heats.The hot fluid section that the liquid outlet of cryogen gas-liquid separator 11 bottoms liquid out enters the cooling heat exchanger 9 of liquefaction ice chest as liquid phase cryogen participates in heat exchange, be cooled to therein-60～-90 ℃, the mixed working fluid stream thigh returning 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 one section of entrance compression of compression that enters again azeotrope compressor 1 behind re-heat to 5～12 ℃ forms azeotrope circulation.
High methane gas liquefaction and split circuit: hot fluid section, dehydrogenation rectifying column 17 charging apertures 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 apertures are connected successively.The phegma entrance of the liquid outlet of a tower overhead gas liquid/gas separator 18 and dehydrogenation rectifying column 17 is connected, and the gas vent of a tower overhead gas liquid/gas separator 18, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger 10, the cold fluid section of the cold fluid section of cooling heat exchanger 9, precool heat exchanger device 8 of cold heat exchanger 16 and 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 phegma entrance of the liquid outlet of No. two tower overhead gas liquid/gas separators and denitrogenation rectifying column 14 is connected, and the gas vent of No. two tower overhead gas liquid/gas separators 13, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger 10, the cold fluid section of the cold fluid section of cooling heat exchanger 9, precool heat exchanger device 8 of cold heat exchanger 16 and connected successively; At the bottom of the tower of denitrogenation rectifying column 14, liquid outlet is connected with the hot fluid section of liquefaction heat exchanger 10.
High methane gas liquefaction and separation process: the high methane gas after purification is chilled in advance through precool heat exchanger device 8 cooling heat exchanger 9 that enters liquefaction ice chest after 5～12 ℃ and is cooled to-60～-90 ℃, enter again after liquefaction heat exchanger 10 is cooled to-135～-155 ℃ and enter 17 rectifying of dehydrogenation rectifying column, dehydrogenation rectifying column 17 overhead gas are carried out gas-liquid separation by cooled with liquid nitrogen to entering a tower overhead gas liquid/gas separator 18 after-165～-180 ℃ in an overhead condensation evaporimeter 19, tower overhead gas liquid/gas separator 18 liquid out returns as phegma and provides cold for dehydrogenation rectifying column 17 from the phegma entrance at dehydrogenation rectifying column 17 tops, tower overhead gas liquid/gas separator 18 top isolated hydrogen content 85%(volumes) above hydrogen-rich gas enters liquid nitrogen subcooler 16 successively, liquefaction heat exchanger 10, cooling heat exchanger 9, precool heat exchanger device 8 provides cold as backflowing cold strand for heat exchanger, the final rich hydrogen production of re-heat to 30～40 ℃ conduct.Dehydrogenation rectifying column 17 still liquid are sent into 14 rectifying of denitrogenation rectifying column after throttling, denitrogenation rectifying column 14 top gas are carried out gas-liquid separation by cooled with liquid nitrogen to entering No. two tower overhead gas liquid/gas separators 13 after-165～-180 ℃ in No. two overhead condensation evaporimeters 12, No. two tower overhead gas liquid/gas separators 13 liquid out returns as phegma and provides cold for denitrogenation rectifying column 14 from the phegma entrance at denitrogenation rectifying column 14 tops, No. two isolated nitrogen-rich gas in tower overhead gas liquid/gas separator 13 tops enter successively liquid nitrogen and cross cold heat exchanger 16, liquefaction heat exchanger 10, cooling heat exchanger 9, precool heat exchanger device 8 provides cold as backflowing cold strand for heat exchanger, the final rich nitrogen product of re-heat to 30～40 ℃ conduct.At the bottom of the tower of denitrogenation rectifying column 14, distillate is-135～-145 ℃, methane content >=98%(volume) liquefied natural gas, return liquefaction heat exchanger 10 be chilled to-160～-170 ℃, after throttling, send into LNG storage tank stores.
Nitrogen refrigerant cycle circuit: hot fluid section, the liquid nitrogen of one section, No. two intercoolers 6 of compression of nitrogen compressor 5, two sections, No. two aftercoolers 7 of compression of nitrogen compressor 5, the hot fluid section of precool heat exchanger device 8, the hot fluid section of cooling heat exchanger 9, liquefaction heat exchanger 10 are crossed cold heat exchanger 16 super cooled sects and connected successively.Liquid nitrogen is crossed the super cooled sect of cold heat exchanger 16 and is connected with the evaporator section of No. two overhead condensation evaporimeters 12, overhead condensation evaporimeter 19 evaporator sections respectively.The evaporator section of No. two overhead condensation evaporimeters 12, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger 10, the cold fluid section of cooling heat exchanger 9, one section of connection successively of nitrogen compressor 5 compression of cold heat exchanger 16.The evaporator section of an overhead condensation evaporimeter 19, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger 10, one section of connection successively of the cold fluid section nitrogen compressor of cooling heat exchanger 95 compression of cold heat exchanger 16.
Nitrogen refrigerant cycle process: nitrogen is pressurized to 1.0～1.8MPa through one section of nitrogen compressor 5 compression and is cooled to 30～50 ℃ by No. two intercoolers 6, enter again two sections of nitrogen compressor 5 compressions and be pressurized to 3.0～4.0MPa, through No. two aftercoolers 7, be cooled to 30～50 ℃ successively, precool heat exchanger device 8 is cooled to after 5～12 ℃, the cooling heat exchanger 9 that enters successively again liquefaction ice chest is cooled to-60～-90 ℃, liquefaction heat exchanger 10 is cooled to-150～-165 ℃, at liquid nitrogen, cross the low temperature hydrogen-rich gas being backflowed in cold heat exchanger 16 again, the rich nitrogen of low temperature and low temperature nitrogen are crossed and are chilled to-165～-180 ℃, finally cross No. two overhead condensation evaporimeters 12 that cold liquid nitrogen enters respectively denitrogenation rectifying column 14, an overhead condensation evaporimeter 19 of dehydrogenation rectifying column 17 provides cold for overhead gas is cooling.Low temperature nitrogen after No. two overhead condensation evaporimeters 12 and overhead condensation evaporimeter 19 liquid nitrogen vaporization is crossed cold heat exchanger 16, liquefaction heat exchanger 10, cooling heat exchanger 9 recovery colds through liquid nitrogen successively, behind re-heat to 7～15 ℃, enter one section of supercharging again of nitrogen compressor 5 compressions, form nitrogen refrigerant cycle.
Chilled brine pipeline: provide cold as cold strand of precool heat exchanger device 8 for it from the chilled brine of 5～9 ℃ of lithium bromide precooling unit, gone out precool heat exchanger device 8 by re-heat to 7～12 ℃.
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, the common practise that this concept is this area.
In addition, it should be noted that, the specific embodiment described in this description, the shape of its parts and components, institute's title of being named etc. 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 ice chest system, nitrogen compressor system; Described azeotrope compressor refrigeration system comprises azeotrope compressor, intercooler, aftercooler, middle knockout drum; Azeotrope compressor has one section of compression and compresses two sections; Described chilldown system comprises precool heat exchanger device, cryogen gas-liquid separator; Described liquefaction ice chest system comprises that 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; At the bottom of the tower of denitrogenation rectifying column, be provided with tower bottom reboiler, 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;
Two sections, No. one aftercooler of compression of one section, No. one intercooler of compression of azeotrope compressor, middle knockout drum, azeotrope compressor, the hot fluid section of precool heat exchanger device, the compound import of cryogen gas-liquid separator are connected successively; The hot fluid section of the hot fluid section of the hot fluid section of the gas vent of cryogen gas-liquid separator, cooling heat exchanger, liquefaction heat exchanger, tower bottom reboiler, liquefaction heat exchanger, the liquefaction cold fluid section of heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The hot fluid section of the liquid outlet of cryogen gas-liquid separator, cooling heat exchanger, the cold fluid section of cooling heat exchanger are connected successively; The cold fluid section of cooling heat exchanger and one section of connection of the compression of azeotrope compressor;
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 phegma entrance of the liquid outlet of a tower overhead gas liquid/gas separator and dehydrogenation rectifying column is connected, and the gas vent of a tower overhead gas liquid/gas separator, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of the cold fluid section of cooling heat exchanger, precool heat exchanger device of cold heat exchanger and 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 phegma entrance of the liquid outlet of No. two tower overhead gas liquid/gas separators and denitrogenation rectifying column is connected, and the gas vent of No. two tower overhead gas liquid/gas separators, liquid nitrogen are crossed super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of the cold fluid section of cooling heat exchanger, precool heat exchanger device of cold heat exchanger and connected successively; At the bottom of the tower of denitrogenation rectifying column, liquid outlet is connected with the hot fluid section of liquefaction heat exchanger;
Hot fluid section, the liquid nitrogen of one section, No. two intercoolers of compression of nitrogen compressor, two sections, No. two aftercoolers of compression of nitrogen compressor, the hot fluid section of precool heat exchanger device, the hot fluid section of cooling heat exchanger, liquefaction heat exchanger are crossed cold heat exchanger super cooled sect and are connected successively; Liquid nitrogen is crossed the super cooled sect of cold heat exchanger and 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 are crossed one section of connection successively of super cooled sect, the liquefaction cold fluid section of heat exchanger, the cold fluid section of cooling heat exchanger, nitrogen compressor compression of cold heat exchanger; The evaporator section of an overhead condensation evaporimeter, liquid nitrogen are crossed one section of connection successively of super cooled sect, the liquefaction cold fluid section of heat exchanger, the compression of the cold fluid section nitrogen compressor of cooling heat exchanger of cold heat exchanger.
2. the device of producing liquefied natural gas and hydrogen-rich gas from coke-stove 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 device described in claim 1 or 2 from high methane gas, to 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 is compressed to and enters an intercooler after 0.8～1.3MPa and be cooled to 30～50 ℃, then in the middle of entering, knockout drum carries out gas-liquid separation; The isolated gas of middle knockout drum continues to enter two sections of entrances of compression of azeotrope compressor, after two sections are compressed to 2.0～4.0MPa, enter again an aftercooler 3 and be cooled to 30～50 ℃, enter again precool heat exchanger device and participate in heat exchange, be cooled to 5～12 ℃; Mixed working fluid after precooling enters and in cryogen gas-liquid separator, carries out gas-liquid separation, the gas that cryogen gas-liquid separator separates goes out enters cooling heat exchanger and participates in heat exchange, after being chilled in advance-60～-90 ℃, enter liquefaction heat exchanger, be cooled to-115～-135 ℃, enter again tower bottom reboiler, thermal source as denitrogenation rectifying column returns to liquefaction heat exchanger after being cooled to-125～-145 ℃, be cooled to-155～-165 ℃, after throttling to 0.23 again～0.43MPa, return to liquefaction heat exchanger, for it provides cold by extremely-65～-95 ℃ of re-heats; The liquid that cryogen gas-liquid separator separates goes out enters cooling heat exchanger section and participates in heat exchange, be cooled to therein-60～-90 ℃, the mixed working fluid stream strand returning with liquefaction heat exchanger after throttling to 0.2～0.4MPa converges merging and oppositely enters cooling heat exchanger, for it provides cold, the one section of entrance compression of compression that enters again azeotrope compressor behind re-heat to 5～12 ℃ 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 ℃ after precool heat exchanger device is chilled to 5～12 ℃ in advance, enter again after liquefaction heat exchanger is cooled to-135～-155 ℃ and enter the rectifying of dehydrogenation rectifying column, dehydrogenation rectifying tower top gaseous body enters a tower overhead gas liquid/gas separator be cooled to-165～-180 ℃ in an overhead condensation evaporimeter after and carries out gas-liquid separation, the liquid that tower overhead gas liquid/gas separator is separated returns to dehydrogenation rectifying column as phegma provides cold for it, No. one the 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 cold strand provides cold for heat exchanger as backflowing, the final rich hydrogen production of re-heat to 30～40 ℃ conduct, the still liquid of dehydrogenation rectifying column is sent into the rectifying of denitrogenation rectifying column after throttling, denitrogenation rectifying column top gas enters No. two tower overhead gas liquid/gas separators be cooled to-165～-180 ℃ in No. two overhead condensation evaporimeters after and carries out gas-liquid separation, No. two isolated liquid of tower overhead gas liquid/gas separator return to denitrogenation rectifying column as phegma provides cold for it, No. two isolated gases of tower overhead gas liquid/gas separator enter successively liquid nitrogen and cross cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger, precool heat exchanger device cold strand provides cold for heat exchanger as backflowing, the final rich nitrogen product of re-heat to 30～40 ℃ conduct, at the bottom of the tower of denitrogenation rectifying column, distillate is-135～-145 ℃, is rich in the liquefied natural gas of methane, returns to liquefaction heat exchanger and is chilled to-160～-170 ℃, sends into LNG storage tank stores after throttling,
Nitrogen refrigerant cycle process: nitrogen is pressurized to 1.0～1.8MPa through one section of nitrogen compressor compression and is cooled to 30～50 ℃ by No. two intercoolers, enter again two sections of nitrogen compressor compressions and be pressurized to 3.0～4.0MPa, through No. two aftercoolers, be cooled to 30～50 ℃ successively, precool heat exchanger device is cooled to after 5～12 ℃, enter successively again cooling heat exchanger and be cooled to-60～-90 ℃, liquefaction heat exchanger is cooled to-150～-165 ℃, at liquid nitrogen, cross in cold heat exchanger and crossed and be chilled to-165～-180 ℃ again, finally cross that cold liquid nitrogen enters respectively No. two overhead condensation evaporimeters and an overhead condensation evaporimeter provides cold for overhead gas is cooling, low temperature nitrogen after No. two overhead condensation evaporimeters and an overhead condensation evaporimeter liquid nitrogen vaporization is crossed cold heat exchanger, liquefaction heat exchanger, cooling heat exchanger recovery cold through liquid nitrogen successively, behind re-heat to 7～15 ℃, enter one section of supercharging again of nitrogen compressor compression, form nitrogen refrigerant cycle.
4. the method for producing liquefied natural gas and rich hydrogen production from high methane gas according to claim 3, is characterized in that: the chilled brine of 5～9 ℃ of take provides cold as cold strand of precool heat exchanger device as it, by re-heat to 7～12 ℃, is gone out precool heat exchanger device.
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