CN104567273A - Expansion and liquefaction method for gas carbon dioxide - Google Patents
Expansion and liquefaction method for gas carbon dioxide Download PDFInfo
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- CN104567273A CN104567273A CN201410704406.8A CN201410704406A CN104567273A CN 104567273 A CN104567273 A CN 104567273A CN 201410704406 A CN201410704406 A CN 201410704406A CN 104567273 A CN104567273 A CN 104567273A
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Abstract
The invention relates to liquefaction of gas carbon dioxide, and particularly discloses an expansion and liquefaction method for gas carbon dioxide. The method comprises the following steps: (a) supercharging gas carbon dioxide containing or not containing gas impurities through a supercharger; (b) cooling the supercharged gas carbon dioxide through a heat exchanger; (c) expanding the cooled gas carbon dioxide through an expander, wherein most gas carbon dioxide is liquefied into a gas-liquid mixture of liquid carbon dioxide and non-liquefied gas carbon dioxide containing or not containing the gas impurities. By adopting the method for liquefying the gas carbon dioxide instead of the conventional way of using low-temperature liquid ammonia, great damage to the life and wealth of people and the surrounding environment due to leakage of ammonia into the atmospheric air is avoided.
Description
Technical field
The liquefaction of relate generally to atmospheric carbon dioxide of the present invention, specifically discloses a kind of expansion liquifying method of atmospheric carbon dioxide.
Background technology
Fig. 2 illustrates a kind of schema of production method of food level liquid carbon dioxide product, comprises the steps:
(1) first compression section 30
0.02MPa will be about from battery limit (BL) external pressure, temperature be 30 ~ 40 DEG C containing micro-mechanical water, methane, ethene, the carbon dioxide content of benzene impurity is about the CO 2 raw material gas body of 99.2% after washing, with stand variable valve 2 that orifice-plate flowmeter 1 controls and reconcile the chemical reaction that enters oxygen mix excessive a little, enter pre-cooler 10 precooling together, the first compression section 30 is entered after the first water separator 20 removes mechanical water, boost to 0.1 ~ 0.35MPa and two section of compression 32 through one section of compression 31 and boost to 0.8 ~ 1.2MPa, from two sections of compressions 32 out containing trace methane, ethene, the carbon dioxide of benzene impurity and the temperature of oxygen excessive are a little 125 ~ 135 DEG C, then de-hydrocarbon operation 50 is delivered to.
(2) de-hydrocarbon operation 50
First entering de-hydrocarbon preheater 51 containing trace methane, ethene, the carbon dioxide of benzene impurity and oxygen excessive a little and be preheating to 215 ~ 225 DEG C from the first compression section 30, then be heated to 480 ~ 520 DEG C through de-hydrocarbon well heater 52, finally enter de-hydrocarbon reactor 53.Methane, ethene and oxygen excessive a little in carbon dioxide containing trace methane, ethene, benzene impurity in de-hydrocarbon reactor 53 issue biochemical reaction, generation carbonic acid gas and water in the effect of High Temperature High Pressure and active ingredient to be platinum and palladium, carrier the be catalyzer of aluminum oxide.When de-hydrocarbon preheater 51 is shell and tube heat exchanger, the shell side of de-hydrocarbon preheater 51 is returned from de-hydrocarbon reactor 53 high-temperature gas out, with tube side from the first compression section 30 containing after trace methane, ethene, the carbon dioxide of benzene impurity and oxygen heat exchange excessive a little, lower the temperature and the second water separator 70 separation machinery water through watercooler 60, enter cleaning section 80.By de-hydrocarbon operation 50, the carbon dioxide containing trace methane, ethene, benzene impurity from the first compression section 30 has become carbonic acid gas and water with the most methane in oxygen excessive a little, ethylene conversion, therefore, enter containing not carrying out the denier methane of chemical reaction, ethene and benzene in the carbon dioxide of cleaning section 80, and trace oxygen and the newly-generated but indissociable micro water vapor of the second water separator 70.De-hydrocarbon well heater 52 can be electric heater.De-hydrocarbon reactor 53 can have the structure of general catalyticreactor.
(3) cleaning section 80
Adopt temperature swing adsorption process, multiple stage cleaner switch operating, when a certain or several cleaners 81 are in adsorbed state, another or several cleaners 82 are in reproduced state, remaining one or several cleaners 83 are in stand-by state, normal temperature adsorbing contaminant, elevated temperature desorption impurity, by the aluminum oxide be seated in cleaner and silica gel absorber to from the second water separator 70 containing denier methane, micro water vapor in the carbon dioxide of ethene and benzene and trace oxygen and water vapour impurity and the selective adsorption of denier benzene impurity, to from the second water separator 70 containing denier methane, the carbon dioxide of ethene and benzene and trace oxygen and water vapour impurity purifies.
1. adsorb
The carbon dioxide containing denier methane, ethene and benzene and trace oxygen and water vapour impurity from the second water separator 70 enters adsorption tower bottom the cleaner 81 being commonly referred to adsorption tower, discharges from the top of adsorption tower.In adsorption tower, sorbent material carries out active adsorption to micro water vapor and denier benzene, the water in the gas of adsorption column outlet end and benzene index is made to reach respective design index or required standard, then the second compression section 40 is delivered to, after adsorbent to certain hour, estimate that sorbent material stops absorption close to time saturated.
2. reversely to bleed off pressure
After adsorption step terminates, the carbon dioxide containing denier methane and ethene and trace oxygen impurity in adsorption tower is discharged outside cleaner 81 against absorption direction current limliting release, terminate pressure in rear adsorption tower close to normal pressure.
3. thermal desorption impurity is added
See the following description to (6) distilation operation 100, after variable valve 1014 throttling expansion, again 0.05MPa is depressurized to from lower heat exchangers 1019 shell side gaseous mixture out, temperature is-18 DEG C, enter electric heater 85 with the combined gas streams of the pressure of discharging from spherical tank 112 to be 1.7MPa temperature the be flashed vapour of-24 DEG C merges together rear formation and be heated to 180 ~ 235 DEG C, enter in the cleaner 81 i.e. adsorption tower that is in and adds thermal desorption impurity step, sorbent material is rinsed in direction against absorption, make adsorbent impurity by heating desorption, sorbent material is fully regenerated, then as exhaust gas emission.
4. sorbent material is cooled
Add after thermal desorption impurity step terminates, adsorbent water in cleaner 81 and benzene impurity almost obtain complete desorb, now, are energized to electric heater 85, make not enter cleaner 81 through electrically heated combined gas streams, the sorbent material in cleaner 81 is cooled to≤25 DEG C.
5. cleaner pressurising
Utilize the carbon dioxide containing denier methane and ethene and trace oxygen impurity oneself switching to from reproduced state a part for the cleaner 82 being commonly referred to adsorption tower of adsorbed state after purifying treatment to be pressurized to adsorptive pressure 0.8 ~ 1.2MPa to cleaner 81, prepare to enter to adsorb next time.
(4) second compression sections 40
The carbon dioxide containing denier methane and ethene and trace oxygen impurity after purifying treatment from cleaning section 80 enters the second compression section 40,2.3-2.8MPa is boosted to through three sections of compressions 41, after cooling, temperature is 28 ~ 32 DEG C, delivers to liquefaction operation 90 and distilation operation 100.
(5) liquefy operation 90
Temperature from the second compression section 40 is 28 ~ 32 DEG C of parts containing the carbon dioxide of denier methane and ethene and trace oxygen impurity enter the reboiler 1011 being commonly referred to tower reactor coil pipe of the distilation tower 101 of distilation operation 100 entrance through orifice-plate flowmeter 1015, thermal source needed for product liquid carbonic acid gas distilation is fully provided, discharge from the outlet of the reboiler 1011 being commonly referred to tower reactor coil pipe, with another part that the temperature from the second compression section 40 is 28 ~ 32 DEG C of carbon dioxides containing denier methane and ethene and trace oxygen impurity, after this another part flows out from the variable valve 1016 controlled by orifice-plate flowmeter 1015, these two portions merge together, the first vaporizer-condenser 91 entering liquefaction operation 90 liquefies.The low-temperature receiver of the first vaporizer-condenser 91 of liquefaction operation 90 is liquefied ammonia, in the first vaporizer-condenser 91, carbon dioxide containing denier methane and ethene and trace oxygen impurity fully and liquefied ammonia carry out thermal exchange, liquefied ammonia liquid level in first vaporizer-condenser 91 is accurately controlled by variable valve, most carbon dioxide is fully liquefied, become-23 ~-24 DEG C of Liquid carbon dioxides, then send into distilation operation 100.
(6) distilation operation 100
The tower reactor being fallen into the distilation tower 101 of distilation operation 100 from the carbonic acid gas of the post liquefaction containing uncooled carbon dioxide and denier methane and ethene and trace oxygen impurity of the first vaporizer-condenser 91 of liquefaction operation 90 by the vaporific spray of shower nozzle 1021 through lower corrugation plate structured packing 1017 carries out distilation, denier methane and ethene and trace oxygen impurity and uncooled carbon dioxide distill from the carbonic acid gas of post liquefaction, be called flashed vapour, the product liquid carbonic acid gas that temperature is-21 ~-23 DEG C is obtained in tower reactor bottom.Flashed vapour rises from tower reactor, first through lower corrugation plate structured packing 1017, fully contact with the low temperature fog-like liquid carbonic acid gas sprayed by shower nozzle 1021 at this, in flashed vapour, the uncooled carbon dioxide of part is condensed and falls in distilation tower 101 tower reactor, flashed vapour continues to rise, through upper corrugation plate structured packing 1018, fully contact with the low temperature fog-like liquid carbonic acid gas fallen from lower heat exchangers 1019 and the tube side of top interchanger 1020 at this, have again the uncooled carbon dioxide of part to be condensed in flashed vapour and fall in distilation tower 101 tower reactor through lower corrugation plate structured packing 1017, flashed vapour continues to rise, enter the tube side of lower heat exchangers 1019, the gaseous mixture be made up of the uncooled carbon dioxide of minute quantity and denier methane and ethene and trace oxygen of discharging from distilation tower 101 top of distilation operation 100, after variable valve 1013 throttling expansion, temperature reduces, enter lower heat exchangers 1019 shell side on distilation tower 101 top, in lower heat exchangers 1019, the flashed vapour entering tube side reduces with temperature after variable valve 1013 throttling expansion the gas mixture with lower temperature entering shell side and carries out heat exchange, having again the uncooled carbon dioxide of part to be condensed in flashed vapour falls in distilation tower 101 tower reactor through upper corrugation plate structured packing 1018 and lower corrugation plate structured packing 1017, flashed vapour continues to rise, enter the tube side of top interchanger 1020, outer low temperature liquefied ammonia enters top interchanger 1020 shell side on distilation tower 101 top, in top interchanger 1020, the flashed vapour entering tube side and the low-temperature liquid ammonia entering shell side carry out heat exchange, have again the uncooled carbon dioxide of part to be condensed and fall in distilation tower 101 tower reactor through the tube side of lower heat exchangers 1019, upper corrugation plate structured packing 1018 and lower corrugation plate structured packing 1017 in flashed vapour, finally, the flashed vapour gaseous mixture be made up of the uncooled carbon dioxide of minute quantity and denier methane and ethene and trace oxygen that becomes that above-mentioned distilation tower 101 top from distilation operation 100 discharges.
(7) cooling working procedure 110 is crossed
The second vaporizer-condenser 111 of cooling working procedure 110 was delivered to from the product liquid carbonic acid gas through distilation in distilation tower 101 tower reactor of distilation operation 100, the low-temperature receiver crossing the second vaporizer-condenser 111 of cooling working procedure 110 is liquefied ammonia, in the second vaporizer-condenser 111, the temperature of product liquid carbonic acid gas enters-and step-down is low, and the product liquid carbonic acid gas being further reduced temperature is delivered to product liquid carbonic acid gas basin 112 through sequencing valve and is stored.
The production method of the food level liquid carbon dioxide product shown in Fig. 2, the low-temperature receiver of the first vaporizer-condenser 91 of liquefaction operation 90 is liquefied ammonia, ammonia has pungent smell, incendivity, easily explodes, and is leaked in air and forms very large harm to life and property and surrounding environment.
Summary of the invention
The present invention will provide the expansion liquifying method of atmospheric carbon dioxide.
The expansion liquifying method of atmospheric carbon dioxide of the present invention, comprises the following steps:
A the pressure of the carbon dioxide contained or not containing gaseous impurities is pressurized to 7.50 ~ 8.50MPa by supercharger by ();
B pressure is that the temperature of containing of 7.50 ~ 8.50MPa or the carbon dioxide not containing gaseous impurities is cooled to 10 DEG C ~ 20 DEG C by interchanger by ();
(c) to be 7.50 ~ 8.50MPa temperature by pressure be 10 DEG C ~ 20 DEG C containing or carbon dioxide containing gaseous impurities be 2.3 ~ 2.7MPa by expander to pressure, temperature is-10 ~-14 DEG C, most carbon dioxides are wherein liquefied, become Liquid carbon dioxide and containing or the gas-liquid mixture of the atmospheric carbon dioxide be not liquefied not containing gaseous impurities.
The expansion liquifying method of atmospheric carbon dioxide of the present invention, carrys out alternative existing low-temperature liquid ammonia with atmospheric carbon dioxide expansion liquefaction and atmospheric carbon dioxide is liquefied, and avoids ammonia and is leaked in air and forms very large harm to life and property and surrounding environment.
Preferably, supercharger is driven by decompressor.
Like this, containing or the energy of carbon dioxide not containing gaseous impurities be fully used.
Preferably, in step (a), be pressurized to 8.00MPa by supercharger, in step (b), be cooled to 15 DEG C by interchanger, in step (c), be 2.5MPa by expander to pressure, temperature is-12 DEG C.
In an embodiment, the carbon dioxide in step (a) is the unstripped gas containing gaseous impurities, before step (a), comprises following sequential steps:
(1) first compression section
CO 2 raw material gas body containing gaseous impurities and the excessive a little oxygen of chemical reaction are entered the first compression section after water separator removing mechanical water, boost to 0.1 ~ 0.35MPa and two section compression through one section of compression and boost to 0.8 ~ 1.2MPa, then deliver to (2) de-hydrocarbon operation;
(2) de-hydrocarbon operation
(2) de-hydrocarbon operation is entered containing the carbon dioxide of gaseous impurities and the excessive a little oxygen of chemical reaction from (1) first compression section, remove containing the methane in the carbon dioxide of gaseous impurities and ethene, then deliver to (3) cleaning section;
(3) cleaning section
Adopt temperature swing adsorption process, multiple stage cleaner switch operating, when a certain or several cleaners are in adsorbed state, remaining cleaner is then in reproduced state, normal temperature adsorbing contaminant, elevated temperature desorption impurity, by the sorbent material be seated in the cleaner of cleaning section to carrying out selective adsorption from (2) de-hydrocarbon operation containing the micro water vapor in the carbon dioxide of gaseous impurities and denier benzene impurity, the carbon dioxide containing gaseous impurities carrying out autospasy hydrocarbon operation is purified, obtain the carbon dioxide containing denier methane and ethene and trace oxygen impurity, then (4) second compression sections are delivered to,
(4) second compression sections
The carbon dioxide containing denier methane and ethene and trace oxygen impurity from (3) cleaning section enters (4) second compression sections, three sections of compressions through (4) second compression sections boost to 5.8 ~ 6.2MPa, 20 ~ 24 DEG C are cooled to through water cooler, then two portions are divided into, a part delivers to the import of the supercharger in step (a), and another part delivers to distilation operation (5);
Wherein, after step (c), comprise the following steps:
(5) distilation operation
The entrance of to be 5.8 ~ 6.2MPa temperature the be carbon dioxide containing denier methane and ethene and trace oxygen impurity of 20 ~ 24 DEG C the enters reboiler of the distilation tower tower reactor of (5) distilation operation of the pressure from (4) second compression sections, thermal source needed for product liquid carbonic acid gas distilation is fully provided,-15 DEG C ~-11 DEG C are down to temperature after the Liquid carbon dioxide heat exchange in purification tower tower reactor, pressure is 2.1 ~ 2.5MPa, discharges from the outlet of reboiler;
The gas-liquid mixture of to be 2.3 ~ 2.7MPa temperature the be Liquid carbon dioxide of-14 ~-10 DEG C of the pressure from step (c) and the atmospheric carbon dioxide be not liquefied containing gaseous impurities, after liquefaction gas-liquid separator separates, methane containing ppm level is sent to the middle part of the distilation tower of (5) distilation operation with the Liquid carbon dioxide of the micro-atmospheric carbon dioxide be not liquefied as being separated liquid afterwards with ethene and the oxygen impurities of ppb level, the tower reactor falling into distilation tower through the structured packing of lower corrugation plate by the vaporific spray of shower nozzle carries out distilation, the methane of the ppm level after being separated in liquid distills out from being separated in rear liquid with the atmospheric carbon dioxide that trace is not liquefied with the oxygen impurities of ethene and ppb level, become flashed vapour, Liquid carbon dioxide in distilation tower tower reactor becomes high purity liquid carbon dioxide product, denier methane forms second combined gas streams as being separated rear gas with the carbon dioxide containing denier methane and ethene and trace oxygen impurity of discharging from the outlet of reboiler with the atmospheric carbon dioxide be not liquefied on a small quantity with ethene and trace oxygen impurity,
In (5) distilation operation, flashed vapour rises from distilation tower tower reactor, successively by the structured packing of lower corrugation plate, the structured packing of upper corrugation plate, the tube side of lower heat exchangers and the tube side of top interchanger, the atmospheric carbon dioxide be not liquefied in flashed vapour is constantly liquefied, fall in distilation tower tower reactor, finally discharge from distilation column overhead, become by uncooled carbon dioxide, methane, the gaseous mixture that ethene and oxygen impurities are formed, then, after the first variable valve throttling expansion, temperature reduces, enter the shell side of lower heat exchangers, from the shell side of lower heat exchangers gaseous mixture out through the second variable valve throttling expansion step-down, rear formation first combined gas streams is merged together with the flashed vapour of discharging from product liquid carbonic acid gas tank top,
Interchanger in step (b) comprises liquefaction watercooler, the first liquefaction heat exchanger and the second liquefaction heat exchanger, the pressure of discharging from the supercharger of step (a) is that the carbon dioxide containing gaseous impurities of 7.50 ~ 8.50MPa is after watercooler cooling, be introduced into the first liquefaction heat exchanger and the first combined gas streams heat exchange, discharge from the first liquefaction heat exchanger, then enter the second liquefaction heat exchanger and the second combined gas streams heat exchange; Enter the electric heater of (3) cleaning section from the first combined gas streams of the first liquefaction heat exchanger discharge, heat through electric heater or do not heat, as adding the gas of thermal desorption impurity or the gas as cooling sorbent material; The imports of three sections of compressions of (4) second compression sections are entered from the second combined gas streams of the second liquefaction heat exchanger discharge.
Like this, the cold of the first combined gas streams and the second combined gas streams is fully used, and saves energy.
Accompanying drawing explanation
Fig. 1 is the schema of the expansion liquifying method of atmospheric carbon dioxide of the present invention;
Fig. 2 is the schema of the production method of existing food level liquid carbon dioxide product;
Embodiment
Be described in detail the embodiment of the expansion liquifying method of atmospheric carbon dioxide of the present invention with reference to the accompanying drawings, the feature and advantage of the expansion liquifying method of atmospheric carbon dioxide of the present invention will become more obvious.
See Fig. 1, the expansion liquifying method of atmospheric carbon dioxide of the present invention, comprises the steps:
(1) first compression section 30
0.02MPa will be about from battery limit (BL) external pressure, temperature be 30 ~ 40 DEG C containing micro-mechanical water, methane, ethene, the carbon dioxide content of benzene impurity is about the CO 2 raw material gas body of 99.2% after washing, with stand variable valve 2 that orifice-plate flowmeter 1 controls and reconcile the chemical reaction that enters oxygen mix excessive a little, enter pre-cooler 10 precooling together, the first compression section 30 is entered after the first water separator 20 removes mechanical water, boost to 0.1 ~ 0.35MPa and two section of compression 32 through one section of compression 31 and boost to 0.8 ~ 1.2MPa, from two sections of compressions 32 out containing trace methane, ethene, the carbon dioxide of benzene impurity and the temperature of oxygen excessive are a little 125 ~ 135 DEG C, then de-hydrocarbon operation 50 is delivered to.
(2) de-hydrocarbon operation 50
First entering de-hydrocarbon preheater 51 containing trace methane, ethene, the carbon dioxide of benzene impurity and oxygen excessive a little and be preheating to 215 ~ 225 DEG C from the first compression section 30, then be heated to 480 ~ 520 DEG C through de-hydrocarbon well heater 52, finally enter de-hydrocarbon reactor 53.Methane, ethene and oxygen excessive a little in carbon dioxide containing trace methane, ethene, benzene impurity in de-hydrocarbon reactor 53 issue biochemical reaction, generation carbonic acid gas and water in the effect of High Temperature High Pressure and active ingredient to be platinum and palladium, carrier the be catalyzer of aluminum oxide.When de-hydrocarbon preheater 51 is shell and tube heat exchanger, the shell side of de-hydrocarbon preheater 51 is returned from de-hydrocarbon reactor 53 high-temperature gas out, with tube side from the first compression section 30 containing after trace methane, ethene, the carbon dioxide of benzene impurity and oxygen heat exchange excessive a little, lower the temperature and the second water separator 70 separation machinery water through watercooler 60, enter cleaning section 80.By de-hydrocarbon operation 50, the carbon dioxide containing trace methane, ethene, benzene impurity from the first compression section 30 has become carbonic acid gas and water with the most methane in oxygen excessive a little, ethylene conversion, therefore, enter containing not carrying out the denier methane of chemical reaction, ethene and benzene in the carbon dioxide of cleaning section 80, and trace oxygen and the newly-generated but indissociable micro water vapor of the second water separator 70.De-hydrocarbon well heater 52 can be electric heater.De-hydrocarbon reactor 53 can have the structure of general catalyticreactor.
(3) cleaning section 80
Adopt temperature swing adsorption process, multiple stage cleaner switch operating, when a certain or several cleaners 81 are in adsorbed state, another or several cleaners 82 are in reproduced state, remaining one or several cleaners 83 are in stand-by state, normal temperature adsorbing contaminant, elevated temperature desorption impurity, by the aluminum oxide be seated in cleaner and silica gel absorber to from the second water separator 70 containing denier methane, micro water vapor in the carbon dioxide of ethene and benzene and trace oxygen and water vapour impurity and the selective adsorption of denier benzene impurity, to from the second water separator 70 containing denier methane, the carbon dioxide of ethene and benzene and trace oxygen and water vapour impurity purifies.
1. adsorb
The carbon dioxide containing denier methane, ethene and benzene and trace oxygen and water vapour impurity from the second water separator 70 enters adsorption tower bottom the cleaner 81 being commonly referred to adsorption tower, discharges from the top of adsorption tower.In adsorption tower, sorbent material carries out active adsorption to micro water vapor and denier benzene, the water in the gas of adsorption column outlet end and benzene index is made to reach respective design index or required standard, obtain the carbon dioxide containing denier methane and ethene and trace oxygen impurity, then the second compression section 40 is delivered to, after adsorbent to certain hour, estimate that sorbent material stops absorption close to time saturated.
2. reversely to bleed off pressure
After adsorption step terminates, the carbon dioxide containing denier methane and ethene and trace oxygen impurity in adsorption tower is discharged outside cleaner 81 against absorption direction current limliting release, terminate pressure in rear adsorption tower close to normal pressure.
3. thermal desorption impurity is added
See the description to (5) liquefaction operation 200 and (6) distilation operation 100, from the first combined gas streams that the first liquefaction heat exchanger 203 is discharged, temperature is about 10 DEG C, enter the electric heater 85 of (3) cleaning section 80, be heated to 180 ~ 235 DEG C, enter in the cleaner 81 i.e. adsorption tower that is in and 4. adds thermal desorption impurity step, sorbent material is rinsed in direction against absorption, make adsorbent impurity by heating desorption, sorbent material is fully regenerated, then as exhaust gas emission.
4. sorbent material is cooled
Add after thermal desorption impurity step terminates, adsorbent water in cleaner 81 and benzene impurity almost obtain complete desorb, now, to electric heater 85 power-off, the temperature of discharging from the first liquefaction heat exchanger 203 is made to be that first combined gas streams of about 10 DEG C enters the electric heater 85 of (3) cleaning section 80 but do not heated, then enter cleaner 81, the sorbent material in cleaner 81 is cooled to≤25 DEG C.
5. cleaner pressurising
Utilize the carbon dioxide containing denier methane and ethene and trace oxygen impurity oneself switching to from reproduced state a part for the cleaner 82 being commonly referred to adsorption tower of adsorbed state after purifying treatment to be pressurized to adsorptive pressure 0.8 ~ 1.2MPa to cleaner 81, prepare to enter to adsorb next time.
(4) second compression sections 40
The carbon dioxide containing denier methane and ethene and trace oxygen impurity after purifying treatment from (3) cleaning section 80 enters (4) second compression sections 40,5.8-6.2MPa is boosted to through three sections of compressions 41, after water cooler 43 cools, temperature is 20 ~ 24 DEG C, after preferred cooling, temperature is 22 DEG C, then two portions are divided into, a part delivers to liquefaction operation 200, and another part delivers to distilation operation 100.
(5) liquefy operation 200
From (4) second compression sections 40 through three sections of compressions 41 boost to 5.8-6.2MPa again after water cooler 43 cools temperature be the carbon dioxide containing denier methane and ethene and trace oxygen impurity of 20 ~ 24 DEG C, 7.05 ~ 8.50MPa is pressurized to through supercharger 201, preferably be pressurized to 8.00MPa, temperature is 104 DEG C, after liquefaction watercooler 202 cools, temperature is down to 32 DEG C, be introduced into the first liquefaction heat exchanger 203, with the first above-mentioned combined gas streams heat exchange, discharge from the first liquefaction heat exchanger 203, then the second liquefaction heat exchanger 204 is entered, with the carbon dioxide containing denier methane and ethene and trace oxygen impurity of being discharged by the outlet from reboiler 1011 and Pressure Drop to the 2.3 ~ 2.7MPa discharged from following liquefied gas liquid/gas separator 206, preferably be down to about 2.5MPa, temperature is down to-10 ~-14 DEG C, the second combined gas streams heat exchange that the divided gas flow of being preferably down to-12 DEG C is formed, temperature is down to 10 DEG C ~ 20 DEG C, preferably be down to 15 DEG C, discharge from the second liquefaction heat exchanger 204, after decompressor 205 expands, Pressure Drop to the 2.3 ~ 2.7MPa of the carbon dioxide containing denier methane and ethene and trace oxygen impurity, preferably be down to about 2.5MPa, temperature is down to-10 ~-14 DEG C, preferably be down to-12 DEG C, most carbon dioxides are wherein liquefied, become the gas-liquid mixture of the Liquid carbon dioxide of the atmospheric carbon dioxide that the oxygen impurities of methane containing ppm level and ethene and ppb level and trace are not liquefied and the atmospheric carbon dioxide be not liquefied containing denier methane and ethene and trace oxygen impurity, after liquefied gas liquid/gas separator 206 is separated, methane wherein containing ppm level is sent to the middle part of the distilation tower 101 of (6) distilation operation 100 with the Liquid carbon dioxide of the micro-atmospheric carbon dioxide be not liquefied as being separated liquid afterwards with ethene and the oxygen impurities of ppb level, the tower reactor being fallen into the distilation tower 101 of distilation operation 100 by the vaporific spray of shower nozzle 1021 through lower corrugation plate structured packing 1017 carries out distilation, denier methane forms above-mentioned second combined gas streams as being separated rear gas with the carbon dioxide containing denier methane and ethene and trace oxygen impurity of discharging from the outlet of reboiler 1011 with the atmospheric carbon dioxide be not liquefied on a small quantity with ethene and trace oxygen impurity.From the second combined gas streams that the second liquefaction heat exchanger 204 is discharged, temperature is about 10 DEG C, enters the import of three sections of compressions 41 of (4) second compression sections 40.From the first combined gas streams that the first liquefaction heat exchanger 203 is discharged, temperature is about 25 DEG C, enters the electric heater 85 of (3) cleaning section 80.
Supercharger 201 is driven by decompressor 205, and the energy containing the carbon dioxide of denier methane and ethene and trace oxygen impurity making three sections of compressions 41 through (4) second compression sections 40 boost to 5.8-6.2MPa is fully used.
(6) distilation operation 100
41 5.8-6.2Mpa is boosted to through three sections of compressions from (4) second compression sections 40, after water cooler 43 cools, temperature is the entrance that the carbon dioxide containing denier methane and ethene and trace oxygen impurity of 20 ~ 24 DEG C enters the reboiler 1011 being commonly referred to tower reactor coil pipe of the distilation tower 101 of (6) distilation operation 100 again, thermal source needed for product liquid carbonic acid gas distilation is fully provided,-15 DEG C ~-11 DEG C are down to temperature after the Liquid carbon dioxide heat exchange in purification tower 101 tower reactor, preferably be down to-13 DEG C, pressure is 2.1 ~ 2.5MPa, be preferably 2.3MPa, discharge from the outlet of the reboiler 1011 being commonly referred to tower reactor coil pipe, the middle part of the distilation tower 101 of (6) distilation operation 100 is sent to from liquid after the separation of the liquefied gas liquid/gas separator 206 of (5) liquefaction operation 200, the tower reactor being fallen into the distilation tower 101 of distilation operation 100 by the vaporific spray of shower nozzle 1021 through lower corrugation plate structured packing 1017 carries out distilation, the atmospheric carbon dioxide that the oxygen impurities of the methane of ppm level and ethene and ppb level and trace are not liquefied distills from the carbonic acid gas of post liquefaction, be called flashed vapour, the product liquid carbonic acid gas that temperature is-21 ~-23 DEG C is obtained in tower reactor bottom.Flashed vapour rises from tower reactor, first through lower corrugation plate structured packing 1017, fully contact with the low temperature fog-like liquid carbonic acid gas sprayed by shower nozzle 1021 at this, in flashed vapour, the uncooled carbon dioxide of part is condensed and falls in distilation tower 101 tower reactor, flashed vapour continues to rise, through upper corrugation plate structured packing 1018, fully contact with the low temperature fog-like liquid carbonic acid gas fallen from lower heat exchangers 1019 and the tube side of top interchanger 1020 at this, have again the uncooled carbon dioxide of part to be condensed in flashed vapour and fall in distilation tower 101 tower reactor through lower corrugation plate structured packing 1017, flashed vapour continues to rise, enter the tube side of lower heat exchangers 1019, the gaseous mixture be made up of the uncooled carbon dioxide of denier and the methane of ppm level and the oxygen impurities of ethene and ppb level of discharging from distilation tower 101 top of distilation operation 100, after variable valve 1013 throttling expansion, temperature reduces, enter lower heat exchangers 1019 shell side on distilation tower 101 top, in lower heat exchangers 1019, the flashed vapour entering tube side reduces with temperature after variable valve 1013 throttling expansion the gas mixture with lower temperature entering shell side and carries out heat exchange, having again the uncooled carbon dioxide of part to be condensed in flashed vapour falls in distilation tower 101 tower reactor through upper corrugation plate structured packing 1018 and lower corrugation plate structured packing 1017, flashed vapour continues to rise, enter the tube side of top interchanger 1020, outer low temperature Liquid carbon dioxide enters top interchanger 1020 shell side on distilation tower 101 top, in top interchanger 1020, the flashed vapour entering tube side and the cryogenic liquid carbonic acid gas entering shell side carry out heat exchange, have again the uncooled carbon dioxide of part to be condensed and fall in distilation tower 101 tower reactor through the tube side of lower heat exchangers 1019, upper corrugation plate structured packing 1018 and lower corrugation plate structured packing 1017 in flashed vapour, finally, the flashed vapour gaseous mixture be made up of the uncooled carbon dioxide of denier and the methane of ppm level and the oxygen impurities of ethene and ppb level that becomes that above-mentioned distilation tower 101 top from distilation operation 100 discharges.After variable valve 1014 throttling expansion, again 0.05MPa is depressurized to from lower heat exchangers 1019 shell side gaseous mixture out, temperature is-18 DEG C, and to be 1.7MPa temperature be that the flashed vapour of-24 DEG C merges together the first above-mentioned combined gas streams of rear formation with the pressure of discharging from product liquid carbonic acid gas basin 112 top.
Product liquid carbonic acid gas in distilation tower 101 tower reactor is delivered to product liquid carbonic acid gas basin 112 through sequencing valve and is stored.
Describing the present invention property and nonrestrictive description according to the embodiment of the present invention, but should be understood that when not departing from relevant scope defined by the claims, those skilled in the art can make and changing and/or amendment.
Claims (4)
1. an expansion liquifying method for atmospheric carbon dioxide, comprises following sequential steps:
A the pressure of the carbon dioxide contained or not containing gaseous impurities is pressurized to 7.50 ~ 8.50MPa by supercharger by ();
B pressure is that the temperature of containing of 7.50 ~ 8.50MPa or the carbon dioxide not containing gaseous impurities is cooled to 10 DEG C ~ 20 DEG C by interchanger by ();
(c) to be 7.50 ~ 8.50MPa temperature by pressure be 10 DEG C ~ 20 DEG C containing or carbon dioxide containing gaseous impurities be 2.3 ~ 2.7MPa by expander to pressure, temperature is-14 ~-10 DEG C, most carbon dioxides are wherein liquefied, become Liquid carbon dioxide and containing or the gas-liquid mixture of the atmospheric carbon dioxide be not liquefied not containing gaseous impurities.
2., according to the expansion liquifying method of atmospheric carbon dioxide according to claim 1, wherein, supercharger is driven by decompressor.
3. according to the expansion liquifying method of the atmospheric carbon dioxide described in claim 1 or 2, wherein, in step (a), 8.00MPa is pressurized to by supercharger, in step (b), be cooled to 15 DEG C, in step (c) by interchanger, be 2.5MPa by expander to pressure, temperature is-12 DEG C.
4. according to the expansion liquifying method of the atmospheric carbon dioxide described in claim 1 or 2, wherein, the carbon dioxide in step (a) is the unstripped gas containing gaseous impurities, before step (a), comprises following sequential steps:
(1) first compression section
CO 2 raw material gas body containing gaseous impurities and the excessive a little oxygen of chemical reaction are entered the first compression section after water separator removing mechanical water, boost to 0.1 ~ 0.35MPa and two section compression through one section of compression and boost to 0.8 ~ 1.2 MPa, then deliver to (2) de-hydrocarbon operation;
(2) de-hydrocarbon operation
(2) de-hydrocarbon operation is entered containing the carbon dioxide of gaseous impurities and the excessive a little oxygen of chemical reaction from (1) first compression section, remove containing the methane in the carbon dioxide of gaseous impurities and ethene, then deliver to (3) cleaning section;
(3) cleaning section
Adopt temperature swing adsorption process, multiple stage cleaner switch operating, when a certain or several cleaners are in adsorbed state, remaining cleaner is then in reproduced state, normal temperature adsorbing contaminant, elevated temperature desorption impurity, by the sorbent material be seated in the cleaner of cleaning section to carrying out selective adsorption from (2) de-hydrocarbon operation containing the micro water vapor in the carbon dioxide of gaseous impurities and denier benzene impurity, the carbon dioxide containing gaseous impurities carrying out autospasy hydrocarbon operation is purified, obtain the carbon dioxide containing denier methane and ethene and trace oxygen impurity, then (4) second compression sections are delivered to,
(4) second compression sections
The carbon dioxide containing denier methane and ethene and trace oxygen impurity from (3) cleaning section enters (4) second compression sections, three sections of compressions through (4) second compression sections boost to 5.8 ~ 6.2MPa, 20 ~ 24 DEG C are cooled to through water cooler, then two portions are divided into, a part delivers to the import of the supercharger in step (a), and another part delivers to distilation operation (5);
Wherein, after step (c), comprise the following steps:
(5) distilation operation
The entrance of to be 5.8 ~ 6.2MPa temperature the be carbon dioxide containing denier methane and ethene and trace oxygen impurity of 20 ~ 24 DEG C the enters reboiler of the distilation tower tower reactor of (5) distilation operation of the pressure from (4) second compression sections, thermal source needed for product liquid carbonic acid gas distilation is fully provided,-15 DEG C ~-11 DEG C are down to temperature after the Liquid carbon dioxide heat exchange in purification tower tower reactor, pressure is 2.1 ~ 2.5MPa, discharges from the outlet of reboiler;
The gas-liquid mixture of to be 2.3 ~ 2.7MPa temperature the be Liquid carbon dioxide of-14 ~-10 DEG C of the pressure from step (c) and the atmospheric carbon dioxide be not liquefied containing gaseous impurities, after liquefaction gas-liquid separator separates, methane containing ppm level is sent to the middle part of the distilation tower of (5) distilation operation with the Liquid carbon dioxide of the micro-atmospheric carbon dioxide be not liquefied as being separated liquid afterwards with ethene and the oxygen impurities of ppb level, the tower reactor falling into distilation tower through the structured packing of lower corrugation plate by the vaporific spray of shower nozzle carries out distilation, the methane of the ppm level after being separated in liquid distills out from being separated in rear liquid with the atmospheric carbon dioxide that trace is not liquefied with the oxygen impurities of ethene and ppb level, become flashed vapour, Liquid carbon dioxide in distilation tower tower reactor becomes high purity liquid carbon dioxide product, denier methane forms second combined gas streams as being separated rear gas with the carbon dioxide containing denier methane and ethene and trace oxygen impurity of discharging from the outlet of reboiler with the atmospheric carbon dioxide be not liquefied on a small quantity with ethene and trace oxygen impurity,
In (5) distilation operation, flashed vapour rises from distilation tower tower reactor, successively by the structured packing of lower corrugation plate, the structured packing of upper corrugation plate, the tube side of lower heat exchangers and the tube side of top interchanger, the atmospheric carbon dioxide be not liquefied in flashed vapour is constantly liquefied, fall in distilation tower tower reactor, finally discharge from distilation column overhead, become by uncooled carbon dioxide, methane, the gaseous mixture that ethene and oxygen impurities are formed, then, after the first variable valve throttling expansion, temperature reduces, enter the shell side of lower heat exchangers, from the shell side of lower heat exchangers gaseous mixture out through the second variable valve throttling expansion step-down, rear formation first combined gas streams is merged together with the flashed vapour of discharging from product liquid carbonic acid gas tank top,
Interchanger in step (b) comprises liquefaction watercooler, the first liquefaction heat exchanger and the second liquefaction heat exchanger, the pressure of discharging from the supercharger of step (a) is that the carbon dioxide containing gaseous impurities of 7.50 ~ 8.50MPa is after watercooler cooling, be introduced into the first liquefaction heat exchanger and the first combined gas streams heat exchange, discharge from the first liquefaction heat exchanger, then enter the second liquefaction heat exchanger and the second combined gas streams heat exchange; Enter the electric heater of (3) cleaning section from the first combined gas streams of the first liquefaction heat exchanger discharge, heat through electric heater or do not heat, as adding the gas of thermal desorption impurity or the gas as cooling sorbent material; The imports of three sections of compressions of (4) second compression sections are entered from the second combined gas streams of the second liquefaction heat exchanger discharge.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106979664A (en) * | 2017-03-06 | 2017-07-25 | 毛恒松 | Atmospheric carbon dioxide liquifying method |
| JP2019063778A (en) * | 2017-10-05 | 2019-04-25 | 住友精化株式会社 | Catalytic oxidation system, and purification method of carbon dioxide |
| CN110090514A (en) * | 2018-01-29 | 2019-08-06 | 株式会社田村制作所 | Gas cleaning plant, method for gas purification and delivery heating device |
| CN111672236A (en) * | 2020-05-19 | 2020-09-18 | 茂名华粤华源气体有限公司 | Preparation method for separating and purifying liquid carbon dioxide |
| CN114768422A (en) * | 2022-04-24 | 2022-07-22 | 惠州凯美特气体有限公司 | Method and equipment for removing impurities by using gaseous carbon dioxide |
| CN115501632A (en) * | 2022-10-19 | 2022-12-23 | 北京石油化工工程有限公司 | Carbon dioxide purification process and carbon dioxide purification system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952111A1 (en) * | 1998-04-24 | 1999-10-27 | Praxair Technology, Inc. | CO2 purification system |
| CN101052852A (en) * | 2004-07-16 | 2007-10-10 | 斯塔托伊尔公司 | Method and device for liquifiing carbon dioxide |
| CN101343061A (en) * | 2008-08-15 | 2009-01-14 | 杭州快凯高效节能新技术有限公司 | Method and apparatus for preparing food level liquid carbon dioxide with flue gas |
| JP4979138B2 (en) * | 2001-01-31 | 2012-07-18 | 株式会社前川製作所 | Dry ice manufacturing method and apparatus |
| CN103058187A (en) * | 2012-12-31 | 2013-04-24 | 惠州凯美特气体有限公司 | Method for producing improved food-grade liquid carbon dioxide product |
-
2014
- 2014-11-27 CN CN201410704406.8A patent/CN104567273A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952111A1 (en) * | 1998-04-24 | 1999-10-27 | Praxair Technology, Inc. | CO2 purification system |
| JP4979138B2 (en) * | 2001-01-31 | 2012-07-18 | 株式会社前川製作所 | Dry ice manufacturing method and apparatus |
| CN101052852A (en) * | 2004-07-16 | 2007-10-10 | 斯塔托伊尔公司 | Method and device for liquifiing carbon dioxide |
| CN101343061A (en) * | 2008-08-15 | 2009-01-14 | 杭州快凯高效节能新技术有限公司 | Method and apparatus for preparing food level liquid carbon dioxide with flue gas |
| CN103058187A (en) * | 2012-12-31 | 2013-04-24 | 惠州凯美特气体有限公司 | Method for producing improved food-grade liquid carbon dioxide product |
Non-Patent Citations (1)
| Title |
|---|
| 郭揆常: "《液化天然气（LNG）工艺与工程》", 31 May 2014 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106979664A (en) * | 2017-03-06 | 2017-07-25 | 毛恒松 | Atmospheric carbon dioxide liquifying method |
| CN106979664B (en) * | 2017-03-06 | 2019-09-20 | 毛恒松 | Atmospheric carbon dioxide liquifying method |
| JP2019063778A (en) * | 2017-10-05 | 2019-04-25 | 住友精化株式会社 | Catalytic oxidation system, and purification method of carbon dioxide |
| JP7017897B2 (en) | 2017-10-05 | 2022-02-09 | 住友精化株式会社 | Catalyzed oxidation system and carbon dioxide purification method |
| CN110090514A (en) * | 2018-01-29 | 2019-08-06 | 株式会社田村制作所 | Gas cleaning plant, method for gas purification and delivery heating device |
| CN111672236A (en) * | 2020-05-19 | 2020-09-18 | 茂名华粤华源气体有限公司 | Preparation method for separating and purifying liquid carbon dioxide |
| CN114768422A (en) * | 2022-04-24 | 2022-07-22 | 惠州凯美特气体有限公司 | Method and equipment for removing impurities by using gaseous carbon dioxide |
| CN115501632A (en) * | 2022-10-19 | 2022-12-23 | 北京石油化工工程有限公司 | Carbon dioxide purification process and carbon dioxide purification system |
| CN115501632B (en) * | 2022-10-19 | 2024-06-04 | 北京石油化工工程有限公司 | Carbon dioxide purification process and carbon dioxide purification system |
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