CN102410704B - Production method of food grade liquid carbon dioxide product for recycling resurgent gases - Google Patents

Production method of food grade liquid carbon dioxide product for recycling resurgent gases Download PDF

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CN102410704B
CN102410704B CN2011102307171A CN201110230717A CN102410704B CN 102410704 B CN102410704 B CN 102410704B CN 2011102307171 A CN2011102307171 A CN 2011102307171A CN 201110230717 A CN201110230717 A CN 201110230717A CN 102410704 B CN102410704 B CN 102410704B
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carbon dioxide
impurity
hydrocarbon
distilation
ethene
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CN102410704A (en
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祝恩福
张晓辉
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HUNAN KAIMEITE GAS CO Ltd
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HUNAN KAIMEITE GAS CO Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • 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
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • 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
    • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F25J2205/70—Heating the adsorption vessel
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/04—Compressor cooling arrangement, e.g. inter- or after-stage cooling or condensate removal
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
    • 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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/10—Boiler-condenser with superposed stages
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids
    • 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
    • F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.

Abstract

The invention relates to a carbon dioxide production method, and particularly discloses a production method of a food grade liquid carbon dioxide product for recycling resurgent gases, which comprises the following steps of: (1) compression process, (2) dealkylation process, (3) purification process, (4) liquefaction process, and (5) distillation and purification process, wherein in the purification process, an impurity heating desorbing step is used for heating the adsorbent, so impurities which are adsorbed by the adsorbent are heated to be desorbed, the adsorbent obtains adequate resurgent gas flow, and a cooling adsorbent step is used for cooling the adsorbent, and the gas flows return to the carbon dioxide raw gas which contains the impurities. Because of the production method of the food grade liquid carbon dioxide product, the contents of methane and ethylene in a food grade liquid carbon dioxide product are greatly reduced, and are lower than the international standard, meanwhile, the resurgent gases of a purification tower are recycled, so the utilization ratio of the carbon dioxide raw gases which contain the impurities is greatly improved and is improved to 88% from 76%, the yield of the food grade liquid carbon dioxide is increased, the production cost is reduced, and the emission of the greenhouse gases is greatly reduced.

Description

A kind of production method of food level liquid carbon dioxide product of reclaiming gas
Technical field
The production method of relate generally to carbon dioxide of the present invention is specifically related to a kind of production method of food level liquid carbon dioxide product of reclaiming gas.
Background technology
Fig. 3 illustrates a kind of flow process of production method of food level liquid carbon dioxide product, comprises the steps:
(1) compression section 30
will be from the mechanical water that contains outside the battery limit (BL), methane, ethene, the carbon dioxide content of the impurity such as benzene is about 99.2% CO 2 raw material gas body through washing and forecooler 10 precoolings, enter compression section 30 after removing mechanical water through the first separator 20, boost to 0.1～0.35Mpa through a stage compressor 31, split-compressor 32 boosts to 0.8～1.2MPa and three-stage blower 33 boosts to 2.3～2.8MPa, from three-stage blower 33 out contain methane, ethene, the temperature of the carbon dioxide of the impurity such as benzene is 110～120 ℃, enter heat exchanger 130, with carry out heat exchange from the heat exchanger 1012 shell sides admixture of gas through again being depressurized to 0.05MPa after control valve 1014 throttling expansions out on distilation tower 101 tops of distilation operation 100 and the combined gas streams that forms heat exchanger 130 after the flashed vapour that spherical tank 112 is discharged merges together, again through water cooler 60 cooling and the second separator 70 separation machinery water, then deliver to cleaning procedure 80.
(2) cleaning procedure 80
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers 81 are in adsorbed state, another or several clarifiers 82 are in reproduced state, remaining one or several 83 of clarifiers are in stand-by state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to the methane that contains from the second separator 70, ethene, minor amount of water steam in the carbon dioxide of the impurity such as benzene (PPM level) and micro-benzene (PPB level) impurity selective absorption, to the methane that contains from the second separator 70, ethene, the carbon dioxide of the impurity such as benzene purifies.
1. absorption
Enter adsorption tower from the carbon dioxide that contains the impurity such as methane, ethene, benzene of the second separator 70 from clarifier 81 bottoms that are commonly referred to adsorption tower, discharge from the top of adsorption tower.In adsorption tower, adsorbent effectively adsorbs minor amount of water steam and micro-benzene etc., make the indexs such as water in the gas of the adsorption tower port of export and benzene reach respective design index or required standard, then deliver to liquefaction operation 90 and distilation operation 100, after adsorbent is adsorbed to certain hour, estimates that adsorbent approaches and stop adsorbing when saturated.
2. reverse bleeding off pressure
After adsorption step finishes, the carbon dioxide that contains the impurity such as trace methane, ethene in adsorption tower is discharged outside clarifier 81 against the release of absorption direction current limliting, the pressure after finishing in adsorption tower is near normal pressure.
3. add thermal desorption impurity
that discharges from distilation tower 101 tops of distilation operation 100 contains a small amount of uncooled carbon dioxide and a large amount of methane, the admixture of gas of ethene, temperature reduces after control valve 1013 throttling expansions, enter heat exchanger 1012 shell sides on distilation tower 101 tops, with the flashed vapour heat exchange of rising in heat exchanger 1012 tube sides, the uncooled carbon dioxide of part in flashed vapour is condensed and falls in distilation tower 101 tower reactors, remaining becomes above-mentioned admixture of gas from the 101 tops discharges of distilation tower, this admixture of gas temperature after control valve 1013 throttling expansions reduces, enter heat exchanger 1012 shell sides on distilation tower 101 tops, again be depressurized to 0.05MPa from heat exchanger 1012 shell sides admixture of gas out after control valve 1014 throttling expansions, a part that merges together the combined gas streams of rear formation with the flashed vapour of discharging from spherical tank 112 enters heat exchanger 130, with be the methane that contains of 110～120 ℃ from three-stage blower 33 temperature out, ethene, entering electric heater 140 after the carbon dioxide heat exchange of the impurity such as benzene is heated and is warming up to 180～235 ℃, entering and being in the clarifier 81 that adds thermal desorption impurity step is in adsorption tower, direction against absorption is rinsed adsorbent, make adsorbent impurity be heated desorb, adsorbent is fully regenerated, then as toxic emission.
4. cooling adsorbent
After adding the end of thermal desorption impurity step, the impurity such as the adsorbent water in clarifier 81 and benzene almost obtain complete desorb, and directly deliver to clarifier 81 with another part of combined gas streams this moment, and the adsorbents in clarifier 81 are cooled to≤25 ℃.
5. clarifier pressurising
The part that switches to the clarifier that is commonly referred to adsorption tower 82 of adsorbed state from reproduced state that is used to control oneself is pressurized to adsorptive pressure 2.3～2.8MPa through the carbon dioxide that contains the impurity such as trace methane, ethene after purified treatment to clarifier 81, prepares to enter absorption next time.
(3) liquefaction operation 90
from the methane that contains after the process purified treatment of cleaning procedure 80, the part of the carbon dioxide of the impurity such as ethene enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, with from the methane that contains after the process purified treatment of cleaning procedure 80, another part of the carbon dioxide of the impurity such as ethene, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.The low-temperature receiver of the first evaporative condenser 91 of liquefaction operation 90 is liquefied ammonia, in the first evaporative condenser 91, the carbon dioxide that contains the impurity such as methane, ethene fully and liquefied ammonia carry out exchange heat, liquefied ammonia liquid level in the first evaporative condenser 91 is accurately controlled by control valve, most carbon dioxide is fully liquefied, become-23～-24 ℃ of liquid CO 2s, then send into distilation operation 100.
(4) the distilation operation 100
Carry out distilation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and the impurity such as methane, ethene of the first evaporative condenser 91 of liquefaction operation 90 by the tower reactor that the vaporific spray of shower nozzle 1021 enters the distilation tower 101 of distilation operation 100, the impurity such as methane, ethene and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain temperature in the tower reactor bottom and be the product liquid carbon dioxide of-21～-23 ℃.Flashed vapour rises from tower reactor, contacts with the fog-like liquid carbon dioxide that sprays from shower nozzle 1021, and the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor; Flashed vapour continues to rise, enter heat exchanger 1012 tube sides on distillation distilation tower 101 tops, with the admixture of gas heat exchange that enters heat exchanger 1012 shell sides after control valve 1013 throttling expansion temperature reductions, the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor.Flashed vapour leaves heat exchanger 1012 tube sides, becomes the admixture of gas that contains a small amount of uncooled carbon dioxide and a large amount of methane, ethene, from the distilation tower 101 tops discharges of distilation operation 100.be 28～32 ℃ from the temperature after the process purified treatment of cleaning procedure 80 and contain trace methane, the part of the carbon dioxide of the impurity such as ethene enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, discharge temperature is-9～-11 ℃, with be 28～32 ℃ from the temperature after the process purified treatment of cleaning procedure 80 and contain trace methane, another part of the carbon dioxide of the impurity such as ethene, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.
(5) cross cooling working procedure 110
Delivered to the second evaporative condenser 111 of cooling working procedure 110 from the product liquid carbon dioxide through distilation in distilation tower 101 tower reactors of distilation operation 100, the low-temperature receiver of crossing the second evaporative condenser 111 of cooling working procedure 110 is liquefied ammonia, in the second evaporative condenser 111, the temperature of product liquid carbon dioxide further reduces, and the product liquid carbon dioxide that is further reduced temperature is delivered to 112 storages of product liquid carbon dioxide basin through sequencing valve.
The production method of food level liquid carbon dioxide product shown in Figure 3 has following shortcoming:
in the production method of food level liquid carbon dioxide product shown in Figure 3, (2) in cleaning procedure 80 3. add thermal desorption impurity step make adsorbent impurity be heated desorb heated air stream used and, (2) the 4. cooling adsorbent step in cleaning procedure 80 is all come since the heat exchanger 1012 shell sides admixture of gas through again being depressurized to 0.05MPa after control valve 1014 throttling expansions out on distilation tower 101 tops of distilation operation 100 and the combined gas streams from forming after the flashed vapour that spherical tank 112 is discharged merges together the adsorbent cooling blast used that is cooled, this combined gas streams 3. add thermal desorption impurity step and after 4. cooling adsorbent step is used by emptying, yet, contained a large amount of carbon dioxide in the gas of emptying, this not only causes the huge waste of unstripped gas, and to a large amount of greenhouse gases of airborne release.
In addition, in the production method of food level liquid carbon dioxide product shown in Figure 3, cleaning procedure 80 carries out after three grades of compressions of compression section 30, the outlet pressure of three-stage blower 33 is up to 2.3～2.8MPa, this just makes equipment, instrument, pipeline and adsorbent etc. in cleaning procedure 80 all work under higher pressure, and the withstand voltage rank that these equipment, instrument, pipeline and adsorbent etc. are proposed is high, has increased the cost input, reduce service life, increased potential safety hazard.
Summary of the invention
The present invention will provide the production method of the food level liquid carbon dioxide product of reclaiming gas.
The production method of the food level liquid carbon dioxide product of a kind of reclaiming gas provided by the invention comprises the following steps:
(1) compression section
CO 2 raw material gas body and the excessive a little oxygen mix of chemical reaction that will contain impurity, with return from cleaning procedure be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enter compression section after the air-flow that is used for cooling adsorbent that cleaning procedure returns is removed mechanical water through separator together, through a stage compressor boost to 0.1～0.35Mpa, split-compressor boosts to 0.8～1.2MPa and three-stage blower 33 boosts to 2.3～2.8MPa, then deliver to and take off the hydrocarbon operation;
(2) take off the hydrocarbon operation
Enter from the carbon dioxide that contains impurity of compression section and the excessive a little oxygen of chemical reaction and take off the hydrocarbon operation, the excessive a little oxygen of methane in taking off hydrocarbon reactor in impurity and ethene and chemical reaction is that 480～520 ℃, pressure are that 2.3～2.8MPa, active component are that platinum and palladium and carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in temperature, generate carbon dioxide and water, remove methane and ethene in the carbon dioxide that contains impurity, then deliver to cleaning procedure;
(3) cleaning procedure
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers are in adsorbed state, another or several clarifiers are in reproduced state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, minor amount of water steam in the carbon dioxide of benzene and steam impurity (PPM level) and micro-benzene (PPB level) impurity selective absorption, to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, the carbon dioxide of benzene and steam impurity purifies, then deliver to liquefaction operation and distilation operation,
Adding in thermal desorption impurity step therein, will make adsorbent impurity be heated desorb for the heating adsorption agent, and the air-flow that adsorbent obtains fully regeneration returns in the CO 2 raw material gas body that contains impurity;
In cooling adsorbent step therein, will return to for the air-flow of cooling adsorbent the CO 2 raw material gas body that contains impurity;
(4) liquefaction operation
enter the entrance of the reboiler that is commonly referred to the tower reactor coil pipe of the distilation tower of distilation operation through orifice flowmeter from the part of the carbon dioxide that contains impurity of cleaning procedure, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of this reboiler, with the another part from the carbon dioxide that contains impurity of cleaning procedure, after this another part flows out from the control valve that is subjected to this orifice flowmeter control, these two parts merge together, the evaporative condenser that enters the liquefaction operation liquefies, the carbon dioxide that major part contains impurity is liquefied, then with the methane of uncooled carbon dioxide with trace, ethene and oxygen are delivered to the distilation operation together,
(5) distilation operation
The distilation tower tower reactor that enters the distilation operation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and trace methane, ethene and oxygen of liquefaction operation is carried out distilation, the impurity such as methane, ethene and oxygen and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain the product liquid carbon dioxide in the tower reactor bottom.
compare with the production method of food level liquid carbon dioxide product shown in Figure 3, the production method of the food level liquid carbon dioxide product of reclaiming gas of the present invention, increase between compression section and cleaning procedure and take off the hydrocarbon operation, simultaneously the thermal desorption impurity step that adds in cleaning procedure is used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration and air-flow that cooling adsorbent step is used for cooling adsorbent returns to the CO 2 raw material gas body that contains impurity, enter compression section after removing mechanical water through separator together with the CO 2 raw material gas that contains impurity, then deliver to and take off the hydrocarbon operation and remove methane and ethene in the carbon dioxide that contains impurity, this not only makes the methane of food level liquid carbon dioxide product and ethylene contents greatly reduce, lower than international standard, and owing to having reclaimed the purifying column regeneration gas, make the CO 2 raw material gas utilization rate that contains impurity greatly improve, be increased to 88% from 76%, increased the output of food level liquid carbon dioxide product, reduced production cost, greatly reduced the discharging of greenhouse gases.
Valuably, from the carbon dioxide that contains impurity of compression section and excessive a little oxygen at first enter take off the hydrocarbon operation take off the hydrocarbon preheater, then through taking off the hydrocarbon heater, enter at last and take off hydrocarbon reactor.
Valuably, taking off the hydrocarbon preheater is tubular heat exchanger, at first the carbon dioxide that contains impurity and excessive a little oxygen from compression section enter the tube side that takes off the hydrocarbon preheater that takes off the hydrocarbon operation, return to from taking off hydrocarbon reactor high-temperature gas out the shell side that takes off the hydrocarbon preheater.
The present invention will provide the production method of the food level liquid carbon dioxide product of another kind of reclaiming gas.
The production method of the food level liquid carbon dioxide product of another kind of reclaiming gas provided by the invention comprises the following steps:
(1) first compression section
CO 2 raw material gas body and the excessive a little oxygen mix of chemical reaction that will contain impurity, with return from cleaning procedure be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enter compression section after the air-flow that is used for cooling adsorbent that cleaning procedure returns is removed mechanical water through separator together, boost to 0.1～0.35MPa and split-compressor boosts to 0.8～1.2MPa through a stage compressor, then deliver to and take off the hydrocarbon operation;
(2) take off the hydrocarbon operation
Enter from the carbon dioxide that contains impurity of the first compression section and the excessive a little oxygen of chemical reaction and take off the hydrocarbon operation, the excessive a little oxygen of methane in taking off hydrocarbon reactor in impurity and ethene and chemical reaction is that 480～520 ℃, pressure are that 0.8～1.2MPa, active component are that platinum and palladium and carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in temperature, generate carbon dioxide and water, remove methane and ethene in the carbon dioxide that contains impurity, then deliver to cleaning procedure;
(3) cleaning procedure
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers are in adsorbed state, another or several clarifiers are in reproduced state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, minor amount of water steam in the carbon dioxide of benzene and steam impurity (PPM level) and micro-benzene (PPB level) impurity selective absorption, to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, the carbon dioxide of benzene and steam impurity purifies, then deliver to the second compression section,
Adding in thermal desorption impurity step therein, will make adsorbent impurity be heated desorb for the heating adsorption agent, and the air-flow that adsorbent obtains fully regeneration returns in the CO 2 raw material gas body that contains impurity;
In cooling adsorbent step therein, will return to for the air-flow of cooling adsorbent the CO 2 raw material gas body that contains impurity;
(4) second compression sections
The carbon dioxide that contains impurity from cleaning procedure enters the second compression section, boosts to 2.3～2.8MPa through the compressor of the second compression section, then delivers to liquefaction operation and distilation operation;
(5) liquefaction operation
enter the entrance of the reboiler that is commonly referred to the tower reactor coil pipe of the distilation tower of distilation operation through orifice flowmeter from the part of the carbon dioxide that contains impurity of the second compression section, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of this reboiler, with the another part from the carbon dioxide that contains impurity of the second compression section, after this another part flows out from the control valve that is subjected to this orifice flowmeter control, these two parts merge together, the evaporative condenser that enters the liquefaction operation liquefies, the carbon dioxide that major part contains impurity is liquefied, then with the methane of uncooled carbon dioxide with trace, ethene and oxygen are delivered to the distilation operation together,
(6) distilation operation
The distilation tower tower reactor that enters the distilation operation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and trace methane, ethene and oxygen of liquefaction operation is carried out distilation, the impurity such as methane, ethene and oxygen and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain the product liquid carbon dioxide in the tower reactor bottom.
the production method of food level liquid carbon dioxide product shown in Figure 2 of the present invention, compression section in the production method of food level liquid carbon dioxide product shown in Figure 1 of the present invention is changed into the first compression section shown in Figure 2 of the present invention and the second compression section, the first compression section is similar to the compression section in the production method of food level liquid carbon dioxide product shown in Figure 1, be positioned at take off hydrocarbon operation and cleaning procedure before, but high output pressure only reaches 0.8～1.2MPa, be starkly lower than the high output pressure 2.3～2.8MPa of the compression section in the production method of food level liquid carbon dioxide product shown in Figure 1, after the second compression section is positioned at and takes off hydrocarbon operation and cleaning procedure, output pressure reaches 2.3～2.8MPa, this just makes and takes off the hydrocarbon operation and cleaning procedure operates under the pressure of 0.8～1.2MPa, do not operate under the pressure of 2.3～2.8MPa cleaning procedure in the production method of food level liquid carbon dioxide product shown in Figure 1 and do not resemble, thereby to taking off the equipment of hydrocarbon operation and cleaning procedure, instrument, pipeline, the withstand voltage rank that catalyst and adsorbent etc. propose is low, reduced the cost input, extended service life, reduced potential safety hazard.
Valuably, from the carbon dioxide that contains impurity of the first compression section and excessive a little oxygen at first enter take off the hydrocarbon operation take off the hydrocarbon preheater, then through taking off the hydrocarbon heater, enter at last and take off hydrocarbon reactor.
Valuably, taking off the hydrocarbon preheater is tubular heat exchanger, at first the carbon dioxide that contains impurity and excessive a little oxygen from the first compression section enter the tube side that takes off the hydrocarbon preheater that takes off the hydrocarbon operation, return to from taking off hydrocarbon reactor high-temperature gas out the shell side that takes off the hydrocarbon preheater.
Description of drawings
Fig. 1 is the flow chart of production method the first embodiment of the food level liquid carbon dioxide product of reclaiming gas of the present invention;
Fig. 2 is the flow chart of production method the second embodiment of the food level liquid carbon dioxide product of reclaiming gas of the present invention;
Fig. 3 is the flow chart of production method of a kind of food level liquid carbon dioxide product of background technology.
The specific embodiment
With reference to the accompanying drawings the specific embodiment of the production method of the food level liquid carbon dioxide product of reclaiming gas of the present invention is described in detail, it is more obvious that the feature and advantage of the production method of the food level liquid carbon dioxide product of reclaiming gas of the present invention will become.
Referring to Fig. 1, the first embodiment of the production method of the food level liquid carbon dioxide product of reclaiming gas of the present invention comprises the steps:
(1) compression section 30
will be from the mechanical water that contains outside the battery limit (BL), methane, ethene, the carbon dioxide content of the impurity such as benzene is about 99.2% CO 2 raw material gas body after washing, with stand control valve 2 that orifice flowmeter 1 controls and reconcile the excessive a little oxygen mix of the chemical reaction that enters, with return from cleaning procedure 80 be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enters together forecooler 10 precoolings from the air-flow that is used for cooling adsorbent that cleaning procedure 80 returns, enter compression section 30 after removing mechanical water through the first separator 20, boost to 0.1～0.35Mpa through a stage compressor 31, split-compressor 32 boosts to 0.8～1.2MPa and three-stage blower 33 boosts to 2.3～2.8MPa, from three-stage blower 33 out contain methane, ethene, the carbon dioxide of the impurity such as benzene and the temperature of oxygen are 110～120 ℃, then deliver to and take off hydrocarbon operation 50.
(2) take off hydrocarbon operation 50
At first enter from the carbon dioxide that contains the impurity such as methane, ethene, benzene of compression section 30 and oxygen and take off hydrocarbon preheater 51 and be preheating to 215～225 ℃, then be heated to 480～520 ℃ through taking off hydrocarbon heater 52, enter at last and take off hydrocarbon reactor 53.Methane, ethene and oxygen in taking off hydrocarbon reactor 53 and contain the carbon dioxide of the impurity such as methane, ethene, benzene is that platinum and palladium, carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in HTHP and active component, generates carbon dioxide and water.When taking off hydrocarbon preheater 51 for tubular heat exchanger, return to from taking off hydrocarbon reactor 53 high-temperature gas out the shell side that takes off hydrocarbon preheater 51, after the carbon dioxide heat exchange that contains the impurity such as methane, ethene, benzene from compression section 30 of tube side, first carry out heat exchange through heat exchanger 130 and following combined gas streams, through water cooler 60 cooling and the second separator 70 separation machinery water, enter cleaning procedure 80 again.By taking off hydrocarbon operation 50, carbon dioxide and water have been become from most methane, conversion of ethylene in the carbon dioxide that contains the impurity such as methane, ethene, benzene of compression section 30, therefore, enter in the carbon dioxide of cleaning procedure 80 and contain trace methane and the ethene that has not removed fully, and trace oxygen and newly-generated but the second indissociable water vapour of separator 70.Take off hydrocarbon heater 52 and can be electric heater.Take off hydrocarbon reactor 53 and can have the structure of general catalytic reactor.
(3) cleaning procedure 80
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers 81 are in adsorbed state, another or several clarifiers 82 are in reproduced state, remaining one or several 83 of clarifiers are in stand-by state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to the trace methane that contains from the second separator 70, ethene, oxygen, minor amount of water steam in the carbon dioxide of the impurity such as benzene and steam (PPM level) and micro-benzene (PPB level) impurity selective absorption, to the trace methane that contains from the second separator 70, ethene, oxygen, the carbon dioxide of the impurity such as benzene and steam purifies.
1. absorption
Enter adsorption tower from the carbon dioxide that contains the impurity such as trace methane, ethene, oxygen, benzene and steam of the second separator 70 from clarifier 81 bottoms that are commonly referred to adsorption tower, discharge from the top of adsorption tower.In adsorption tower, adsorbent effectively adsorbs minor amount of water steam and micro-benzene etc., make the indexs such as water in the gas of the adsorption tower port of export and benzene reach respective design index or required standard, then deliver to liquefaction operation 90 and distilation operation 100, after adsorbent is adsorbed to certain hour, estimates that adsorbent approaches and stop adsorbing when saturated.
2. reverse bleeding off pressure
After adsorption step finishes, the carbon dioxide that contains the impurity such as trace methane, ethene, oxygen in adsorption tower is discharged outside clarifier 81 against the release of absorption direction current limliting, the pressure after finishing in adsorption tower is near normal pressure.
3. add thermal desorption impurity
that discharges from distilation tower 101 tops of distilation operation 100 contains a small amount of uncooled carbon dioxide and a large amount of methane, ethene, the admixture of gas of oxygen, temperature reduces after control valve 1013 throttling expansions, enter heat exchanger 1012 shell sides on distilation tower 101 tops, with the flashed vapour heat exchange of rising in heat exchanger 1012 tube sides, the uncooled carbon dioxide of part in flashed vapour is condensed and falls in distilation tower 101 tower reactors, remaining becomes above-mentioned admixture of gas from the 101 tops discharges of distilation tower, this admixture of gas temperature after control valve 1013 throttling expansions reduces, enter heat exchanger 1012 shell sides on distilation tower 101 tops, again be depressurized to 0.05MPa from heat exchanger 1012 shell sides admixture of gas out after control valve 1014 throttling expansions, a part that merges together the combined gas streams of rear formation with the flashed vapour of discharging from spherical tank 112 enters heat exchanger 130, with the trace methane that contains that takes off hydrocarbon preheater 51 that comes autospasy hydrocarbon operation 50, ethene, oxygen, entering electric heater 140 after the carbon dioxide heat exchange of the impurity such as benzene and steam is heated and is warming up to 180～235 ℃, entering and being in the clarifier 81 that adds thermal desorption impurity step is in adsorption tower, direction against absorption is rinsed adsorbent, make adsorbent impurity be heated desorb, adsorbent is fully regenerated, then return from the mechanical water that contains outside the battery limit (BL), methane, ethene, the carbon dioxide content of the impurity such as benzene is about in 99.2% CO 2 raw material gas body.
4. cooling adsorbent
After adding the end of thermal desorption impurity step, the impurity such as the adsorbent water in clarifier 81 and benzene almost obtain complete desorb, directly deliver to clarifier 81 with another part of combined gas streams this moment, adsorbents in clarifier 81 are cooled to≤25 ℃, then return from the carbon dioxide content that contains the impurity such as mechanical water, methane, ethene, benzene outside the battery limit (BL) and be about in 99.2% CO 2 raw material gas body.
5. clarifier pressurising
Be used to an own part that switches to the clarifier that is commonly referred to adsorption tower 82 of adsorbed state from reproduced state and through the carbon dioxide that contains the impurity such as trace methane, ethene and oxygen after purified treatment, clarifier 81 be pressurized to adsorptive pressure 2.3～2.8MPa, prepare to enter absorption next time.
(4) liquefaction operation 90
the trace methane that contains from cleaning procedure 80, the part of the carbon dioxide of the impurity such as ethene and oxygen enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, with from the trace methane that contains after the process purified treatment of cleaning procedure 80, another part of the carbon dioxide of the impurity such as ethene and oxygen, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.The low-temperature receiver of the first evaporative condenser 91 of liquefaction operation 90 is liquefied ammonia, in the first evaporative condenser 91, the carbon dioxide that contains the impurity such as trace methane, ethene and oxygen fully and liquefied ammonia carry out exchange heat, liquefied ammonia liquid level in the first evaporative condenser 91 is accurately controlled by control valve, most carbon dioxide is fully liquefied, become-23～-24 ℃ of liquid CO 2s, then send into distilation operation 100.
(5) the distilation operation 100
Carry out distilation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and the impurity such as trace methane, ethene and oxygen of the first evaporative condenser 91 of liquefaction operation 90 by the tower reactor that the vaporific spray of shower nozzle 1021 enters the distilation tower 101 of distilation operation 100, the impurity such as methane, ethene and oxygen and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain temperature in the tower reactor bottom and be the product liquid carbon dioxide of-21～-23 ℃.Flashed vapour rises from tower reactor, contacts with the fog-like liquid carbon dioxide that sprays from shower nozzle 1021, and the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor; Flashed vapour continues to rise, enter heat exchanger 1012 tube sides on distillation distilation tower 101 tops, with the admixture of gas heat exchange that enters heat exchanger 1012 shell sides after control valve 1013 throttling expansion temperature reductions, the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor.Flashed vapour leaves heat exchanger 1012 tube sides, becomes the admixture of gas that contains a small amount of uncooled carbon dioxide and a large amount of methane, ethene, from the distilation tower 101 tops discharges of distilation operation 100.be 28～32 ℃ from the temperature after the process purified treatment of cleaning procedure 80 and contain trace methane, the part of the carbon dioxide of the impurity such as ethene and oxygen enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, discharge temperature is-9～-11 ℃, with be 28～32 ℃ from the temperature after the process purified treatment of cleaning procedure 80 and contain trace methane, another part of the carbon dioxide of the impurity such as ethene and oxygen, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.
(6) cross cooling working procedure 110
Delivered to the second evaporative condenser 111 of cooling working procedure 110 from the product liquid carbon dioxide through distilation in distilation tower 101 tower reactors of distilation operation 100, the low-temperature receiver of crossing the second evaporative condenser 111 of cooling working procedure 110 is liquefied ammonia, in the second evaporative condenser 111, the temperature of product liquid carbon dioxide further reduces, and the product liquid carbon dioxide that is further reduced temperature is delivered to 112 storages of product liquid carbon dioxide basin through sequencing valve.
Referring to Fig. 2, the second embodiment of the production method of the food level liquid carbon dioxide product of reclaiming gas of the present invention comprises the steps:
(1) first compression section 300
will be from the mechanical water that contains outside the battery limit (BL), methane, ethene, the carbon dioxide content of the impurity such as benzene is about 99.2% CO 2 raw material gas body after washing, with stand control valve 2 that orifice flowmeter 1 controls and reconcile the excessive a little oxygen mix of the chemical reaction that enters, with return from cleaning procedure 80 be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enters together forecooler 10 precoolings from the air-flow that is used for cooling adsorbent that cleaning procedure 80 returns, enter the first compression section 300 after removing mechanical water through the first separator 20, boost to 0.1～0.35Mpa and split-compressor 32 boosts to 0.8～1.2MPa through a stage compressor 31, from split-compressor 32 out contain methane, ethene, the carbon dioxide of the impurity such as benzene and the temperature of oxygen are 125～135 ℃, then deliver to and take off hydrocarbon operation 50.
(2) take off hydrocarbon operation 50
At first enter from the carbon dioxide that contains the impurity such as methane, ethene, benzene of the first compression section 300 and oxygen and take off hydrocarbon preheater 51 and be preheating to 215～225 ℃, then be heated to 480～520 ℃ through taking off hydrocarbon heater 52, enter at last and take off hydrocarbon reactor 53.Methane, ethene and oxygen in taking off hydrocarbon reactor 53 and contain the carbon dioxide of the impurity such as methane, ethene, benzene is that platinum and palladium, carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in HTHP and active component, generates carbon dioxide and water.When taking off hydrocarbon preheater 51 for tubular heat exchanger, return to from taking off hydrocarbon reactor 53 high-temperature gas out the shell side that takes off hydrocarbon preheater 51, after the carbon dioxide heat exchange that contains the impurity such as methane, ethene, benzene from the first compression section 300 of tube side, first carry out heat exchange through heat exchanger 130 and following combined gas streams, through water cooler 60 cooling and the second separator 70 separation machinery water, enter cleaning procedure 80 again.By taking off hydrocarbon operation 50, carbon dioxide and water have been become from most methane, conversion of ethylene in the carbon dioxide that contains the impurity such as methane, ethene, benzene of the first compression section 300, therefore, enter in the carbon dioxide of cleaning procedure 80 and contain trace methane and the ethene that has not removed fully, and trace oxygen and newly-generated but the second indissociable water vapour of separator 70.Take off hydrocarbon heater 52 and can be electric heater.Take off hydrocarbon reactor 53 and can have the structure of general catalytic reactor.
(3) cleaning procedure 80
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers 81 are in adsorbed state, another or several clarifiers 82 are in reproduced state, remaining one or several 83 of clarifiers are in stand-by state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to the trace methane that contains from the second separator 70, ethene, oxygen, minor amount of water steam in the carbon dioxide of the impurity such as benzene and steam (PPM level) and micro-benzene (PPB level) impurity selective absorption, to the trace methane that contains from the second separator 70, ethene, oxygen, the carbon dioxide of the impurity such as benzene and steam purifies.
1. absorption
Enter adsorption tower from the carbon dioxide that contains the impurity such as trace methane, ethene, oxygen, benzene and steam of the second separator 70 from clarifier 81 bottoms that are commonly referred to adsorption tower, discharge from the top of adsorption tower, in adsorption tower, adsorbent effectively adsorbs minor amount of water steam and micro-benzene etc., make the indexs such as water in the gas of the adsorption tower port of export and benzene reach respective design index or required standard, then deliver to the second compression section 150, after adsorbent is adsorbed to certain hour, estimates that adsorbent approaches and stop adsorbing when saturated.
2. reverse bleeding off pressure
After adsorption step finishes, the carbon dioxide that contains the impurity such as trace methane, ethene, oxygen in adsorption tower is discharged outside clarifier 81 against the release of absorption direction current limliting, the pressure after finishing in adsorption tower is near normal pressure.
3. add thermal desorption impurity
that discharges from distilation tower 101 tops of distilation operation 100 contains a small amount of uncooled carbon dioxide and a large amount of methane, ethene, the admixture of gas of oxygen, temperature reduces after control valve 1013 throttling expansions, enter heat exchanger 1012 shell sides on distilation tower 101 tops, with the flashed vapour heat exchange of rising in heat exchanger 1012 tube sides, the uncooled carbon dioxide of part in flashed vapour is condensed and falls in distilation tower 101 tower reactors, remaining becomes above-mentioned admixture of gas from the 101 tops discharges of distilation tower, this admixture of gas temperature after control valve 1013 throttling expansions reduces, enter heat exchanger 1012 shell sides on distilation tower 101 tops, again be depressurized to 0.05MPa from heat exchanger 1012 shell sides admixture of gas out after control valve 1014 throttling expansions, a part that merges together the combined gas streams of rear formation with the flashed vapour of discharging from spherical tank 112 enters heat exchanger 130, with the trace methane that contains that takes off hydrocarbon preheater 51 that comes autospasy hydrocarbon operation 50, ethene, oxygen, entering electric heater 140 after the carbon dioxide heat exchange of the impurity such as benzene and steam is heated and is warming up to 180～235 ℃, entering and being in the clarifier 81 that adds thermal desorption impurity step is in adsorption tower, direction against absorption is rinsed adsorbent, make adsorbent impurity be heated desorb, adsorbent is fully regenerated, then return from the mechanical water that contains outside the battery limit (BL), methane, ethene, the carbon dioxide content of the impurity such as benzene is about in 99.2% CO 2 raw material gas body.
4. cooling adsorbent
After adding the end of thermal desorption impurity step, the impurity such as the adsorbent water in clarifier 81 and benzene almost obtain complete desorb, directly deliver to clarifier 81 with another part of combined gas streams this moment, adsorbents in clarifier 81 are cooled to≤25 ℃, then return from the carbon dioxide content that contains the impurity such as mechanical water, methane, ethene, benzene outside the battery limit (BL) and be about in 99.2% CO 2 raw material gas body.
5. clarifier pressurising
The part that switches to the clarifier that is commonly referred to adsorption tower 82 of adsorbed state from reproduced state that is used to control oneself is pressurized to adsorptive pressure 0.8～1.2MPa through the carbon dioxide that contains the impurity such as trace methane, ethene and oxygen after purified treatment to clarifier 81, prepares to enter absorption next time.
(4) second compression sections 150
Enter the second compression section 150 from the carbon dioxide that contains the impurity such as trace methane, ethene and oxygen after the process purified treatment of cleaning procedure 80, compressed machine 151 boosts to 2.3～2.8MPa, temperature is 28～32 ℃ after cooling, delivers to liquefaction operation 90 and distilation operation 100.
(5) liquefaction operation 90
be that 28～32 ℃ and distilation operation 100 temperature are-9～-11 ℃ and contain trace methane from the temperature of the second compression section 150, the part of the carbon dioxide of the impurity such as ethene and oxygen enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, be 28～32 ℃ with temperature from the second compression section 150 and contain trace methane, another part of the carbon dioxide of the impurity such as ethene and oxygen, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.The low-temperature receiver of the first evaporative condenser 91 of liquefaction operation 90 is liquefied ammonia, in the first evaporative condenser 91, the carbon dioxide that contains the impurity such as trace methane, ethene and oxygen fully and liquefied ammonia carry out exchange heat, liquefied ammonia liquid level in the first evaporative condenser 91 is accurately controlled by control valve, most carbon dioxide is fully liquefied, become-23～-24 ℃ of liquid CO 2s, then send into distilation operation 100.
(6) the distilation operation 100
Carry out distilation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and the impurity such as trace methane, ethene and oxygen of the first evaporative condenser 91 of liquefaction operation 90 by the tower reactor that the vaporific spray of shower nozzle 1021 enters the distilation tower 101 of distilation operation 100, the impurity such as methane, ethene and oxygen and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain temperature in the tower reactor bottom and be the product liquid carbon dioxide of-21～-23 ℃.Flashed vapour rises from tower reactor, contacts with the fog-like liquid carbon dioxide that sprays from shower nozzle 1021, and the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor; Flashed vapour continues to rise, enter heat exchanger 1012 tube sides on distillation distilation tower 101 tops, with the admixture of gas heat exchange that enters heat exchanger 1012 shell sides after control valve 1013 throttling expansion temperature reductions, the uncooled carbon dioxide of the part in flashed vapour is condensed, and falls in tower reactor.Flashed vapour leaves heat exchanger 1012 tube sides, becomes the admixture of gas that contains a small amount of uncooled carbon dioxide and a large amount of methane, ethene, from the distilation tower 101 tops discharges of distilation operation 100.be 28～32 ℃ from the temperature of the second compression section 150 and contain trace methane, the part of the carbon dioxide of the impurity such as ethene and oxygen enters the entrance of the reboiler that is commonly referred to the tower reactor coil pipe 1011 of the distilation tower 101 of distilation operation 100 through orifice flowmeter 1015, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of the reboiler 1011 that is commonly referred to the tower reactor coil pipe, discharge temperature is-9～-11 ℃, be 28～32 ℃ with temperature from the second compression section 150 and contain trace methane, another part of the carbon dioxide of the impurity such as ethene and oxygen, after this another part flows out from the control valve 1016 that is subjected to orifice flowmeter 1015 controls, these two parts merge together, the first evaporative condenser 91 that enters liquefaction operation 90 liquefies.
(7) cross cooling working procedure 110
Delivered to the second evaporative condenser 111 of cooling working procedure 110 from the product liquid carbon dioxide through distilation in distilation tower 101 tower reactors of distilation operation 100, the low-temperature receiver of crossing the second evaporative condenser 111 of cooling working procedure 110 is liquefied ammonia, in the second evaporative condenser 111, the temperature of product liquid carbon dioxide further reduces, and the product liquid carbon dioxide that is further reduced temperature is delivered to 112 storages of product liquid carbon dioxide basin through sequencing valve.
Describing the present invention property and nonrestrictive description according to the embodiment of the present invention, but should be understood that in the situation that do not break away from relevant protection domain defined by the claims, those skilled in the art can make change and/or revise.

Claims (6)

1. the production method of the food level liquid carbon dioxide product of a reclaiming gas, comprise the following steps:
(1) compression section
CO 2 raw material gas body and the excessive a little oxygen mix of chemical reaction that will contain impurity, with return from cleaning procedure be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enter compression section after the air-flow that is used for cooling adsorbent that cleaning procedure returns is removed mechanical water through separator together, through a stage compressor boost to 0.1～0.35Mpa, split-compressor boosts to 0.8～1.2MPa and three-stage blower 33 boosts to 2.3～2.8MPa, then deliver to and take off the hydrocarbon operation;
(2) take off the hydrocarbon operation
Enter from the carbon dioxide that contains impurity of compression section and the excessive a little oxygen of chemical reaction and take off the hydrocarbon operation, the excessive a little oxygen of methane in taking off hydrocarbon reactor in impurity and ethene and chemical reaction is that 480～520 ℃, pressure are that 2.3～2.8MPa, active component are that platinum and palladium and carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in temperature, generate carbon dioxide and water, remove methane and ethene in the carbon dioxide that contains impurity, then deliver to cleaning procedure;
(3) cleaning procedure
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers are in adsorbed state, another or several clarifiers are in reproduced state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, PPM level steam in the carbon dioxide of benzene and steam impurity and the selective absorption of PPB level benzene impurity, to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, the carbon dioxide of benzene and steam impurity purifies, then deliver to liquefaction operation and distilation operation,
Adding in thermal desorption impurity step therein, will make adsorbent impurity be heated desorb for the heating adsorption agent, and the air-flow that adsorbent obtains fully regeneration returns in the CO 2 raw material gas body that contains impurity;
In cooling adsorbent step therein, will return to for the air-flow of cooling adsorbent the CO 2 raw material gas body that contains impurity;
(4) liquefaction operation
enter the entrance of the reboiler that is commonly referred to the tower reactor coil pipe of the distilation tower of distilation operation through orifice flowmeter from the part of the carbon dioxide that contains impurity of cleaning procedure, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of this reboiler, with the another part from the carbon dioxide that contains impurity of cleaning procedure, after this another part flows out from the control valve that is subjected to this orifice flowmeter control, these two parts merge together, the evaporative condenser that enters the liquefaction operation liquefies, the carbon dioxide that major part contains impurity is liquefied, then with the methane of uncooled carbon dioxide with trace, ethene and oxygen are delivered to the distilation operation together,
(5) distilation operation
The distilation tower tower reactor that enters the distilation operation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and trace methane, ethene and oxygen of liquefaction operation is carried out distilation, methane, ethene and oxygen impurities and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain the product liquid carbon dioxide in the tower reactor bottom.
2. according to the production method of the food level liquid carbon dioxide product of reclaiming gas claimed in claim 1, it is characterized in that: from the carbon dioxide that contains impurity of compression section and excessive a little oxygen at first enter take off the hydrocarbon operation take off the hydrocarbon preheater, then through taking off the hydrocarbon heater, enter at last and take off hydrocarbon reactor.
3. according to the production method of the food level liquid carbon dioxide product of reclaiming gas claimed in claim 2, it is characterized in that: taking off the hydrocarbon preheater is tubular heat exchanger, at first the carbon dioxide that contains impurity and excessive a little oxygen from compression section enter the tube side that takes off the hydrocarbon preheater that takes off the hydrocarbon operation, return to from taking off hydrocarbon reactor high-temperature gas out the shell side that takes off the hydrocarbon preheater.
4. the production method of the food level liquid carbon dioxide product of a reclaiming gas, comprise the following steps:
(1) first compression section
CO 2 raw material gas body and the excessive a little oxygen mix of chemical reaction that will contain impurity, with return from cleaning procedure be used for the heating adsorption agent, make adsorbent impurity be heated desorb, adsorbent obtains the air-flow of fully regeneration or enter compression section after the air-flow that is used for cooling adsorbent that cleaning procedure returns is removed mechanical water through separator together, boost to 0.1～0.35Mpa and split-compressor boosts to 0.8～1.2MPa through a stage compressor, then deliver to and take off the hydrocarbon operation;
(2) take off the hydrocarbon operation
Enter from the carbon dioxide that contains impurity of the first compression section and the excessive a little oxygen of chemical reaction and take off the hydrocarbon operation, the excessive a little oxygen of methane in taking off hydrocarbon reactor in impurity and ethene and chemical reaction is that 480～520 ℃, pressure are that 0.8～1.2MPa, active component are that platinum and palladium and carrier are that the effect of the catalyst of aluminium oxide issues biochemical reaction in temperature, generate carbon dioxide and water, remove methane and ethene in the carbon dioxide that contains impurity, then deliver to cleaning procedure;
(3) cleaning procedure
adopt temperature swing adsorption process, many clarifier switch operatings, when a certain or several clarifiers are in adsorbed state, another or several clarifiers are in reproduced state, normal temperature absorption impurity, high temperature desorption impurity, by being seated in aluminium oxide in clarifier and silica gel absorber to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, PPM level steam in the carbon dioxide of benzene and steam impurity and the selective absorption of PPB level benzene impurity, to coming the trace methane that contains of autospasy hydrocarbon operation, ethene, oxygen, the carbon dioxide of benzene and steam impurity purifies, then deliver to the second compression section,
Adding in thermal desorption impurity step therein, will make adsorbent impurity be heated desorb for the heating adsorption agent, and the air-flow that adsorbent obtains fully regeneration returns in the CO 2 raw material gas body that contains impurity;
In cooling adsorbent step therein, will return to for the air-flow of cooling adsorbent the CO 2 raw material gas body that contains impurity;
(4) second compression sections
The carbon dioxide that contains impurity from cleaning procedure enters the second compression section, boosts to 2.3-2.8MPa through the compressor of the second compression section, then delivers to liquefaction operation and distilation operation;
(5) liquefaction operation
enter the entrance of the reboiler that is commonly referred to the tower reactor coil pipe of the distilation tower of distilation operation through orifice flowmeter from the part of the carbon dioxide that contains impurity of the second compression section, fully provide product liquid carbon dioxide distilation required thermal source, discharge from the outlet of this reboiler, with the another part from the carbon dioxide that contains impurity of the second compression section, after this another part flows out from the control valve that is subjected to this orifice flowmeter control, these two parts merge together, the evaporative condenser that enters the liquefaction operation liquefies, the carbon dioxide that major part contains impurity is liquefied, then with the methane of uncooled carbon dioxide with trace, ethene and oxygen are delivered to the distilation operation together,
(6) distilation operation
The distilation tower tower reactor that enters the distilation operation from the carbon dioxide after the liquefaction that contains uncooled carbon dioxide and trace methane, ethene and oxygen of liquefaction operation is carried out distilation, methane, ethene and oxygen impurities and uncooled carbon dioxide distill from the carbon dioxide after liquefaction, be called flashed vapour, obtain the product liquid carbon dioxide in the tower reactor bottom.
5. according to the production method of the food level liquid carbon dioxide product of reclaiming gas claimed in claim 4, it is characterized in that: from the carbon dioxide that contains impurity of the first compression section and excessive a little oxygen at first enter take off the hydrocarbon operation take off the hydrocarbon preheater, then through taking off the hydrocarbon heater, enter at last and take off hydrocarbon reactor.
6. according to the production method of the food level liquid carbon dioxide product of reclaiming gas claimed in claim 5, it is characterized in that: taking off the hydrocarbon preheater is tubular heat exchanger, at first the carbon dioxide that contains impurity and excessive a little oxygen from the first compression section enter the tube side that takes off the hydrocarbon preheater that takes off the hydrocarbon operation, return to from taking off hydrocarbon reactor high-temperature gas out the shell side that takes off the hydrocarbon preheater.
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