CN104515362B - Method for producing liquid carbon dioxide - Google Patents
Method for producing liquid carbon dioxide Download PDFInfo
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- CN104515362B CN104515362B CN201310460724.XA CN201310460724A CN104515362B CN 104515362 B CN104515362 B CN 104515362B CN 201310460724 A CN201310460724 A CN 201310460724A CN 104515362 B CN104515362 B CN 104515362B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 239000007788 liquid Substances 0.000 title claims abstract description 158
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 105
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 122
- 239000002994 raw material Substances 0.000 claims abstract description 91
- 239000003507 refrigerant Substances 0.000 claims description 76
- 238000000926 separation method Methods 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 230000001172 regenerating effect Effects 0.000 claims description 23
- 230000008929 regeneration Effects 0.000 claims description 19
- 238000011069 regeneration method Methods 0.000 claims description 19
- 239000002808 molecular sieve Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002203 pretreatment Methods 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 230000002779 inactivation Effects 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 87
- 229960004424 carbon dioxide Drugs 0.000 description 73
- 239000003921 oil Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 239000002826 coolant Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 230000003009 desulfurizing effect Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 241000208340 Araliaceae Species 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 235000008434 ginseng Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The invention provides a method for producing liquid carbon oxide. The method comprises an expanding step, a first gas-liquid separating step, a liquefying step and a heat exchange step. The method disclosed by the invention can be used for treating carbon dioxide raw material gas flow, especially the carbon dioxide raw material gas flow with relatively high carbon dioxide concentration (for example, the concentration of carbon dioxide is over 70mol%), obviously increasing the yield of the liquid carbon dioxide, lowering the production cost of the liquid carbon dioxide and improving the overall yield of the process.
Description
Technical field
The present invention relates to a kind of method producing liquid CO 2.
Background technology
A large amount of discharges of GHG carbon dioxide are considered as the one of the main reasons causing global warming.According to system
Meter, the CO2 emissions of China in 2012 have exceeded 8,000,000,000 tons.The use of a large amount of Fossil fuels creates many low concentrations
CO2Gas.In addition, creating the carbon dioxide of a large amount of higher concentrations in many chemical industry process, such as：With coal it is
The conversion process of raw material ammonia, methanol or hydrogen.Reclaim these carbon dioxide, the discharge capacity of carbon dioxide can not only be reduced, reduce
The environmental problem causing because atmospheric carbon dioxide levels steeply rise, and can also by the carbon dioxide reclaiming recycling
Produce certain economic benefit.For example, the carbon dioxide reclaiming is used as oil displacement agent, in injection oil reservoir, crude oil can be made to expand, fall
Low viscosity of crude, reduces residual oil saturation, improves oil recovery factor, particularly in tertiary oil recovery technology, carbon dioxide quilt
Prove one of maximally efficient intensified oil reduction oil displacement agent.
At present, the commercial run reclaiming carbon dioxide mainly includes chemical absorption method, oxygen-rich combustion method and low-temperature liquefaction method
Deng.Wherein, low-temperature liquefaction method is that CO 2 raw material gas are forced into after 1.5-3.0MPa, uses cooling medium（As liquefied ammonia, liquid
Propylene）Absorbing latent heat, so that carbon dioxide is liquefied, thus preparing liquid CO 2.
However, when adopting existing low-temperature liquefaction technique productions liquid CO 2, there is a problem of that production cost is high.Cause
This, the production cost how reducing low-temperature liquefaction technique remains a technical problem urgently to be resolved hurrily.
Content of the invention
It is an object of the invention to solving the life existing during the existing technique productions liquid CO 2 by low-temperature liquefaction
The technical problem of high cost, provides a kind of method by low-temperature liquefaction technique productions liquid CO 2, this method reduces
Its production cost, is obtained in that higher economic benefit.
The invention provides a kind of method producing liquid CO 2, the method includes expansion step, the first gas-liquid is divided
From step, liquefaction step and heat exchange steps：
In described expansion step, the CO 2 raw material gas stream of precooling is expanded, logistics after being expanded, institute
The pressure stating the CO 2 raw material gas stream of precooling is to be not less than 4MPa；
In described first gas-liquid separation step, isolate not condensate logistics after described expansion, obtain the first gas phase
Logistics and first liquid carbon dioxide；
In described liquefaction step, the atmospheric carbon dioxide liquefaction in described first gaseous stream obtains containing liquid two
The logistics of carbonoxide；
In described heat exchange steps, by CO 2 raw material gas stream and described first liquid carbon dioxide and/or
The logistics containing liquid CO 2 obtaining in liquefaction step carries out heat exchange, obtains the CO 2 raw material gas of described precooling
Stream and product liquid carbon dioxide.
Using the method for the present invention to CO 2 raw material gas stream, particularly gas concentration lwevel higher（As carbon dioxide
Concentration is 70 moles of more than %）CO 2 raw material gas stream processed, the yield of liquid CO 2 can be significantly improved,
Reduce the production cost of liquid CO 2, improve the overall income of technical process.
Brief description
Fig. 1 is used for a kind of embodiment of the method for the present invention is described.
Fig. 2 is used for a kind of embodiment being more highly preferred to of the method for the present invention is described.
Fig. 3 is the technological process for comparative example 1 production liquid CO 2 is described.
Description of reference numerals
1：Gas-liquid separation tower 2：Compressor
3：Removing oil tower 4：Desulfurizing tower
5：Dehydrating tower 6：Dehydrating tower
7：Heat exchanger 8：Heat exchanger
9：Liquefier 10：Gas-liquid separation tower
11：Pump 12：Heat exchanger
13：Product 14：Compressor
15：Diverter 16：Choke valve
17：Heat exchanger 18：Gas-liquid separation tower
19：Pump 20：Blender
21：Heat exchanger 22：Choke valve
23：Choke valve 24：Gas-liquid separation tower
25：Pump 26：Heat exchanger
27：Heat exchanger 28：Gas-liquid separation tower
Specific embodiment
The invention provides a kind of method producing liquid CO 2, the method includes expansion step, the first gas-liquid is divided
From step, liquefaction step and heat exchange steps：
In described expansion step, the CO 2 raw material gas stream of precooling is expanded, logistics after being expanded, institute
The pressure stating the CO 2 raw material gas stream of precooling is to be not less than 4MPa；
In described first gas-liquid separation step, isolate not condensate logistics after described expansion, obtain the first gas phase
Logistics and first liquid carbon dioxide；
In described liquefaction step, the atmospheric carbon dioxide liquefaction in described first gaseous stream obtains containing liquid two
The logistics of carbonoxide；
In described heat exchange steps, by CO 2 raw material gas stream and described first liquid carbon dioxide and/or
The logistics containing liquid CO 2 obtaining in liquefaction step carries out heat exchange, obtains the CO 2 raw material gas of described precooling
Stream and product liquid carbon dioxide.
The method according to the invention, the logistics containing liquid CO 2 that described liquefaction step obtains is according to specifically used feelings
Condition can export it is also possible to carry out purification further, to improve the purity of liquid CO 2.In described CO 2 raw material gas
Stream also contain other gases, and mainly critical temperature is less than the gas of carbon dioxide, during as nitrogen, liquefaction step obtain containing liquid
The logistics of body carbon dioxide also contains gas, and when these gases need to remove, the method according to the invention can also include：?
Carry out the second gas-liquid separation step, in described second gas-liquid separation step, from described containing liquid two after described liquefaction step
Isolate not condensate in the logistics of carbonoxide, obtain the second gaseous stream and second liquid carbon dioxide, so that described
By CO 2 raw material gas stream and described first liquid carbon dioxide and/or described second liquid dioxy in heat exchange steps
Change carbon logistics and carry out heat exchange.
In the present invention, the method for gas-liquid separation can be the conventional selection of this area, such as gravity separation, centrifugation point
From method, silk screen partition method and ultra-filtration and separation method.
In described expansion step, the pressure of described CO 2 raw material gas stream is to be not less than 4MPa.In described carbon dioxide
When the pressure of flow of feed gas is less than 4MPa, the temperature separating the gaseous stream obtaining after one side throttling expansion is relatively low（Typically
For -50 DEG C to -70 DEG C）, less than some refrigerants（As liquefied ammonia）Operating temperature, be difficult to realize liquefaction；On the other hand it is easy to
Form Solid dry ice, disabling facility and pipeline.Although the gas phase obtaining after throttling expansion can be controlled by adjusting expansion ratio
The temperature of logistics simultaneously avoids the formation of dry ice, but yield that is such and being difficult to the final liquid CO 2 of raising, thus reducing liquid
The cost of body carbon dioxide.The pressure of described CO 2 raw material gas stream is preferably below 15MPa, such as below 12MPa.
Preferably, the pressure of described CO 2 raw material gas stream is to be not less than 5MPa, such as 5-15MPa, so passes through to expand
Enable to the partial CO 2 liquefaction in CO 2 raw material gas stream, on the one hand expanded after the temperature of gaseous stream that obtains
Degree can be matched with the operating temperature of conventional various refrigerants, and wherein do not exist or be substantially not present dry ice；Another
Aspect can also improve the yield of liquid CO 2.Preferably, the pressure of described CO 2 raw material gas stream is not preferably low
In 6MPa, more preferably it is not less than the critical pressure of carbon dioxide（That is, 7.382MPa）, so it is obtained in that and to improve further
Liquid CO 2 yield.It is highly preferred that the pressure of described CO 2 raw material gas stream is the critical pressure higher than carbon dioxide,
If the critical pressure higher than carbon dioxide is to 15MPa.Specifically, the pressure of described CO 2 raw material gas stream can be 7.5MPa
More than, such as 8-12MPa.
The temperature of described CO 2 raw material gas stream can be suitable in liquefaction step, atmospheric carbon dioxide liquefy
Temperature.Preferably, the temperature of described CO 2 raw material gas stream is to be near the critical temperature of carbon dioxide, for example, can be
20-50℃.And described precool CO 2 raw material gas stream temperature can be -20 DEG C to 20 DEG C, preferably -10 DEG C to 10 DEG C.
Water content in described CO 2 raw material gas stream is different with the source of CO 2 raw material gas stream, can be normal
Rule select.Usually, the water content in described CO 2 raw material gas stream make described CO 2 raw material gas stream dew point be-
45 DEG C to -50 DEG C.Described dew point is the pressure in 0.1MPa（In terms of gauge pressure）Lower mensure.
Depending on the source with this CO 2 raw material gas stream for the gas concentration lwevel in described CO 2 raw material gas stream.This
The method of invention is particularly suitable for producing liquid CO 2 by the higher flow of feed gas of gas concentration lwevel.Preferably, described two
In raw material of carbon oxide air-flow, the concentration of carbon dioxide is 70 moles of more than %, such as 70-95 mole of %.It is highly preferred that described titanium dioxide
In carbon raw material air-flow, the concentration of carbon dioxide is 80 moles of more than %, and such as 85-95 mole of % so can reduce further and run
Energy expenditure in journey, thus reduce operating cost further.
Described CO 2 raw material gas stream can be obtained using various approach.In one embodiment, hand in described heat
Change CO 2 raw material gas stream and described first liquid carbon dioxide and/or containing of obtaining in liquefaction step in step
Before the logistics of liquid CO 2 carries out heat exchange, described CO 2 raw material gas stream can be obtained by pre-treatment step.
In described pre-treatment step, carbonated air-flow being pressurized, the air-flow after supercharging being optionally dehydrated, thus obtaining
Described CO 2 raw material gas stream.
Described carbonated air-flow can derive from the various chemical industry process that can produce carbon dioxide, its tool
Body example can include but is not limited to：Fossil fuel（As coal, oil and natural gas）Combustion process produce flue gas；By from
Carbon dioxide enriched air-flow obtained from trapping carbon dioxide in described flue gas；And with coal for the change of raw material ammonia, methanol or hydrogen
Change the carbon dioxide gas stream of process generation.Preferably, described carbonated air-flow is by trapping two from described flue gas
Carbon dioxide enriched air-flow obtained from carbonoxide or oxygen-enriched combusting；And with coal for the conversion process of raw material ammonia, methanol or hydrogen
The carbon dioxide gas stream producing.
The mode of described supercharging can be the conventional selection of this area.For example, it is possible to by compression, preferred multi-stage compression Lai
Described carbonated air-flow is pressurized.The condition of described supercharging makes two that the pressure of the air-flow after supercharging is sufficient so that
The pressure of raw material of carbon oxide air-flow meets the requirement of expansion step.
The condition of described dehydration typically makes the dew point of described CO 2 raw material gas stream be -45 DEG C to -50 DEG C.Described de-
The mode of water can be the conventional selection of this area, for example：Gas-liquid separation is made by gravitational settling, thus realizing being dehydrated；Pass through
Centrifugation makes gas-liquid separation, thus realizing being dehydrated；Condensed by making water at low temperature, thus realizing being dehydrated；By being pressurized
Air-flow afterwards is contacted under dehydration conditions with dehydrant, thus realizing being dehydrated.
In the preferred embodiment of the present invention, can be under dehydration conditions, by the air-flow after supercharging and dehydrant
Contact, thus realize being dehydrated.Described dehydrant can be conventional various dehydrants, preferably molecular sieve.
This preferred embodiment in, described dehydration conditions can be according to the source of CO 2 raw material gas and dehydration
The concrete species of agent is selected.Usually, when described dehydrant is molecular sieve, described dehydration can be in 20-50 DEG C of temperature
Carry out under degree.
Generally molecular sieve due to reaching adsorption equilibrium, and can be difficult to acquisition and satisfactorily take off after used a period of time
Water effect, needs to be regenerated.Usually, molecular sieve is accomplished by proceeding to regenerative process after carrying out the dehydration of 6-12h.Therefore, exist
When molecular sieve is used as dehydrant, the method according to the invention can also include the regeneration step that molecular sieve is regenerated.
In regeneration step, can at regeneration conditions the molecular sieve of inactivation be contacted with regenerating medium, so that the molecular sieve of inactivation
Activity recovery.
The hydrolysis that described regeneration condition be enough to make absorption in molecular sieve surface and duct is inhaled, and the water of desorbing is carried
Out, and regenerating medium itself will not occur condensation to be defined, can be selected according to the concrete species of regenerating medium.Typically
Ground, described regeneration condition includes：Temperature can be more than 200 DEG C, such as 200-350 DEG C；In terms of gauge pressure, pressure can be 2-
5MPa.
Described regenerating medium can be the conventional selection of this area, and at least partly described regenerating medium comes from described second
Gaseous stream and/or a part of described CO 2 raw material gas stream.For example：The CO 2 raw material gas that can will obtain after dehydration
As regenerating medium after part heating in stream, the 5-10 in the CO 2 raw material gas stream that typically will obtain after dehydration rubs
Your % uses as regenerating medium.
When the second gaseous stream also including the second gas-liquid separation step and obtaining in the method for the present invention is mainly nitrogen,
Preferably described second gaseous stream is used as described regenerating medium（That is, in regeneration step, at least part of regenerating medium comes from institute
State the second gaseous stream）.When CO 2 raw material gas stream after will be partially dehydrated is as regenerating medium, this as regenerating medium
Partial CO 2 flow of feed gas is after regeneration step output in addition it is also necessary to be re-fed into pre-treatment step being pressurized and being taken off
Water, increased the burden of pre-treatment step.Described second gaseous stream can be reduced as regenerating medium as regenerating medium
CO 2 raw material gas stream amount, CO 2 raw material gas stream is not even used as regenerating medium, effectively mitigates pretreatment
The burden of step, improves the effective treating capacity of pre-treatment step.
When using described second gaseous stream as at least part of regenerating medium, can be using conventional method by the second gas
Phase logistics and heating media for heat exchange, thus improve the temperature of the second gaseous stream so as to meet the requirement of regeneration step.Described plus
Thermal medium is generally water vapour.Supercharging in described pre-treatment step is to be pressurized the mode of carbonated air-flow compression
When, the outlet streams of compressor generally require and are cooled down.Therefore, it can described second gaseous stream as described compressor
Outlet cooling medium, so can reduce the outlet streams temperature of compressor, the temperature of the second gaseous stream can be improved again, subtract
The consumption of heating medium and outlet cooling medium is it might even be possible to eliminate the demand for heating medium and outlet cooling medium less.
After the outlet streams heat exchange with compressor, when temperature still cannot meet the requirement of regeneration step, can by with compressor
The second gaseous stream after outlet streams heat exchange carries out heat exchange with heating medium further, thus meeting the requirement of regeneration step.
Described heating medium can be for example the regenerating medium of regeneration step output（That is, the regeneration after being contacted with the molecular sieve of inactivation is situated between
Matter）And/or water vapour.
In the present invention, described heat exchange is indirect heat exchange, can carry out in conventional heat-exchanger rig.For example：Described heat exchange
Can carry out in conventional shell-and-tube heat exchanger.
As needed, in described pre-treatment step, the air-flow after supercharging is carried out removing oil, desulfurization and/or dehydration, obtains
Described CO 2 raw material gas stream.Preferably, before described dehydration, the air-flow after supercharging can be carried out removing oil and/or desulfurization,
To remove hydrocarbons and sulphur-containing substance in the air-flow after supercharging（As hydrogen sulfide）.The method of described removing oil and desulfurization can be
The conventional selection of this area.Usually, described removing oil can be realized by being contacted with de-oiling agent, described desulfurization can by with
Desulfurization agent and realize.Described de-oiling agent and desulfurizing agent can be each that the conventional of this area selects.Usually, described removing oil
Agent can be activated carbon, and described desulfurizing agent can be zinc oxide.
In the present invention, described expansion refers to the adiabatic process being changed logistics from high pressure to lower pressure direction.Described swollen
Swollen can carry out in the common various devices being capable of above-mentioned transformation, for example：Choke valve and decompressor.In decompressor
When carrying out described expansion, energy loss is lower, and therefore described expansion is carried out preferably in decompressor.
The expansion ratio of described expansion can be 1.5-8, preferably 2-6, more preferably 3-5.Expansion ratio in described expansion
When being within above range, enable to 25-70 mole of % in CO 2 raw material gas stream by expanding（Preferably 30 moles % with
On, more preferably 40 moles more than %）Atmospheric carbon dioxide be changed into liquid CO 2, can mitigate liquefaction step place
Good balance is obtained between reason amount and the energy loss expanding generation.Described expansion ratio refer to expand after logistics volume with swollen
The ratio of the volume of swollen front logistics.
In described liquefaction step, can be using various methods commonly used in the art by the carbon dioxide in the first gaseous stream
Liquefaction.Specifically, can be by refrigerant and described first gaseous stream heat exchange, so that the gas in described first gaseous stream
Co 2 liquefaction.
Described refrigerant can be the various liquid that under conditions of described heat exchange, can gasify after absorbing heat, can
Think the conventional selection of this area, such as one or more of liquefied ammonia, liquid CO 2 and liquid propene.
Ratio between described refrigerant and described first gaseous stream can be according to the species of the refrigerant using
And liquefaction condition is selected.Usually, when described refrigerant is liquefied ammonia, refrigerant and described first gaseous stream
Between mol ratio can be 0.05-0.3：1；When described refrigerant is liquid propene, refrigerant and described first gas
Mol ratio between phase logistics can be 0.1-0.8：1；When described refrigerant is liquid CO 2, refrigerant and institute
Stating the mol ratio between the first gaseous stream can be 0.15-0.9：1.
The condition of refrigerant and described first gaseous stream heat exchange is can make the gas dioxy in the first gaseous stream
Change that carbon is whole or the substantially all liquid that is converted into is defined, can be selected according to the species of refrigerant.Usually, described
When refrigerant is liquefied ammonia, the temperature of refrigerant can be -30 DEG C to -50 DEG C, and in terms of absolute pressure, pressure can be 0.04MPa
To 0.22MPa；When described refrigerant is liquid CO 2, the temperature of refrigerant can be -30 DEG C to -50 DEG C, with
Absolute pressure meter, pressure can be 0.65-2.5MPa；When described refrigerant is liquid propene, the temperature of refrigerant can for-
30 DEG C to -50 DEG C, in terms of absolute pressure, pressure can be 0.07MPa to 0.26MPa.
At least partly existing in gaseous form in refrigerant after the heat exchange of output in liquefaction step, can be by wherein
The refrigerant being existed with gas is again transformed into liquid Posterior circle and uses.Now, the method according to the invention can also be wrapped
Include refrigerant recycling step, in described refrigerant recycling step, can after making heat exchange refrigerant with for dropping
The cooling medium heat exchange of low refrigerant temperature, thus the gas in refrigerant after heat exchange is transformed into liquid again.Institute
State cooling medium to select for conventional.Usually, as cooling after the part in refrigerant after heat exchange being cooled down
Medium uses.
In practical operation, after refrigerant after heat exchange being pressurized, it is divided into A, B two streams, wherein, by B
Logistics is directly cooled down, and A logistics then can be sent in heat exchanger as cooling medium using after conventional method cooling, with
B logistics carries out heat exchange, makes the gas transition in B logistics become liquid.The ratio of A, B two streams can be according to specific heat exchange
Condition is selected.Usually, the mol ratio between A logistics and B logistics can be 1：0.2-0.7.The liquid being formed by B logistics
Can send in liquefaction step as refrigerant.The 3rd gaseous stream and can be separated into the A logistics after B logistics heat exchange
Three liquid phase streams, wherein, the 3rd liquid phase stream can also be sent in liquefaction step as refrigerant, and the 3rd gaseous stream then returns
Return in refrigerant recovery system and recycle.
Can be sent directly into liquefaction step after cooling down further from the refrigerant of refrigerant recovery system output.
Preferably, after the expanded cooling of refrigerant of refrigerant recovery system output, send in liquefaction step.By refrigerant
The temperature that the expansion ratio being expanded is controlled to the refrigerant after expanding disclosure satisfy that the use requirement of liquefaction step is defined.
Usually, the pressure from the refrigerant of refrigerant recovery system output is 1.5-10MPa（Gauge pressure）, expanded
When, expansion ratio can be 3-60.
The present invention one kind preferred embodiment in, refrigerant is sent into before described liquefaction step（Including will make
Cold medium expand when, be refrigerant is expanded before）, described refrigerant is made with after the heat exchange of described liquefaction step output
Cold medium carries out heat exchange.By with the heat exchange exporting from liquefaction step after refrigerant carry out heat exchange, can reduce i.e. further
The temperature of the refrigerant of liquefaction step will be entered.Specifically, will be laggard for refrigerant heat exchange after refrigerant and described heat exchange
Row expands, and can significantly reduce the gas content in the logistics after expansion, increases the effective of the refrigerant entering liquefaction step
Amount, improves the cooling effectiveness of liquefaction step.
Second liquid carbon dioxide that second gas-liquid separation step obtains and the first gas-liquid separation step obtain
First liquid carbon dioxide can be used as output of products.
The method according to the invention, in described heat exchange steps, by CO 2 raw material gas stream and described first liquid
Carbon dioxide and/or the logistics containing liquid CO 2 obtaining in liquefaction step carry out heat exchange, obtain described pre-cooling
But CO 2 raw material gas stream and product liquid carbon dioxide, to reduce the temperature of described CO 2 raw material gas stream, so
The temperature of the carbon dioxide feed stream of expansion step can be lowered into further, the liquid improving in logistics after expanding contains
Amount.Preferably, in described second gas-liquid separation step, isolate not condensate from the described logistics containing liquid CO 2,
Obtain the second gaseous stream and second liquid carbon dioxide, by described CO 2 raw material gas stream and described first liquid two
Carbonoxide logistics and/or described second liquid carbon dioxide carry out heat exchange, obtain the carbon dioxide raw material of described precooling
Air-flow and product liquid carbon dioxide.
The method according to the invention, in described heat exchange steps, the temperature of the CO 2 raw material gas stream of described precooling
Spend for -20 DEG C to 20 DEG C, preferably -10 DEG C are 10 DEG C.
Fig. 1 shows a kind of embodiment of the method for the present invention.With reference to Fig. 1, this embodiment to be described.
As shown in figure 1, carbonated air-flow is separated off most of liquid substance in gas-liquid separation tower 1, then
Enter in compressor 2 and be pressurized to more than 4MPa（As 5-15MPa, the preferably not lower than critical pressure of carbon dioxide, more preferably
Critical pressure higher than carbon dioxide）.Air-flow after supercharging optionally passes sequentially through removing oil tower 3 and desulfurizing tower 4, removes hydrocarbon therein
Class material and sulfur-containing compound（Mainly hydrogen sulfide）Afterwards, enter dehydrating tower 5（Dehydrating tower 5 and dehydrating tower 6 be alternately dehydrated and
Regeneration, in the state shown in Fig. 1, dehydrating tower 5 is in dewatering work pattern, and dehydrating tower 6 is in reproduction operation pattern）In taken off
Water, the dew point of air-flow is reduced to and is within the scope of -45 DEG C to -50 DEG C.Wherein, the absorbent in removing oil tower 3 is usually
Activated carbon, the absorbent in desulfurizing tower 4 is usually zinc oxide, and the dehydrant in dehydrating tower 5 is usually molecular sieve.
From the CO 2 raw material gas stream of dehydrating tower 5 output, a part（Typically constitute from the 5- of CO 2 raw material gas stream total amount
10 moles of %）After being heated to regeneration temperature as regenerating medium in heat exchanger 26, send into the molecule in dehydrating tower 6, with inactivation
Sieve contact, so that the molecular sieve activity recovery of inactivation, subsequently enters cooling down in heat exchanger 27, and in gas-liquid separation tower 28
In be separated off liquid after, reenter in compressor 2 and be pressurized.
Remainder from the CO 2 raw material gas stream of dehydrating tower 5 output then enters and carries out pre-cooling in heat exchanger 12
But, subsequently into choke valve 23（Can be with other expansion gears, such as decompressor replaces）In expanded, will expand after material give
Enter in gas-liquid separation tower 24 and carry out gas-liquid separation, obtain the first gaseous stream and first liquid carbon dioxide.First gas phase
Logistics subsequently enters and carries out heat exchange with refrigerant in liquefier 9 so that the atmospheric carbon dioxide in the first gaseous stream liquefies,
Obtain refrigerant after logistics and the heat exchange containing liquid CO 2.
Logistics containing liquid CO 2 enters in gas-liquid separation tower 10, is separated off not condensate（Predominantly nitrogen）, obtain
To the second gaseous stream and second liquid carbon dioxide.
The first liquid carbon dioxide of gas-liquid separation tower 24 output and the second liquid two of gas-liquid separation tower 10 output
Carbonoxide logistics converges in feeding heat exchanger 12 through pump 25 and pump 11 respectively, after CO 2 raw material gas stream heat exchange, as
Product 13 exports.
After the heat exchange of liquefier 9 output, refrigerant enters in refrigerant recycling step, after being again transformed into liquid
Recycle.In refrigerant recycling step, after after heat exchange, refrigerant compresses in compressor 14, enter in diverter 15
It is divided into A, B two streams, B logistics is directly entered in heat exchanger 17, choke valve 16 is then passed through in A logistics（Can be expanded with other
Device, such as decompressor replace）Heat exchanger 17 is entered as cooling medium after carrying out expanding cooling, will be cold for the gas in B logistics
But become liquid.The A logistics entering heat exchanger 17 as cooling medium subsequently enters in gas-liquid separation tower 18, is separated into the
Three gaseous streams and the 3rd liquid phase stream, wherein, the 3rd gaseous stream is re-fed into being compressed Posterior circle in compressor 14 making
With, after the 3rd liquid phase stream is then mixed with the liquid phase stream being formed by B logistics through pump 19 in blender 20, sending into heat exchanger
In 21 with come from after refrigerant heat exchange after the heat exchange of liquefier 9, by choke valve 22（Can be with other expansion gears, such as
Decompressor replaces）Expand cooling Posterior circle further to enter in liquefier 9.
Fig. 2 shows a kind of embodiment being more highly preferred to of the method for the present invention.As shown in Fig. 2 being more highly preferred at this
Embodiment in, will second gaseous stream send into compressor 2 in as outlet cooling medium change with the outlet streams of compressor 2
After heat, enter in heat exchanger 8 and carry out heat exchange with the regenerating medium coming from dehydrating tower 6, subsequently enter in heat exchanger 7 and add
Thermal medium（Generally water vapour）Heat exchange, makes the second gaseous stream temperature reach regeneration temperature, subsequently in dehydrating tower 6, right
The molecular sieve of inactivation is regenerated, and exports finally by heat exchanger 8.
Various industrial occasions be can be used for by liquid CO 2 prepared by the method for the present invention, for example：As oil displacement agent
In injection oil reservoir；Send in various industrial process as solvent, cold-producing medium or raw material.
Describe the present invention with reference to embodiments in detail.
In following examples and comparative example, using ASPEN analog systemss, technological process is simulated.
In following examples and comparative example, if not otherwise specified, pressure is gauge pressure.
Embodiment 1-13 is used for the method for the present invention is described.
Embodiment 1
Liquid CO 2 is produced using the technological process shown in Fig. 2.
In carbonated air-flow, the mean concentration of carbon dioxide is 88 moles of %, the average dew of carbon dioxide containing air flow
Point is 40 DEG C, and the mean concentration of nitrogen is 11 moles of %.Carbonated air-flow is sent into gas-liquid with the speed of 34223kg/h
In knockout tower 1.The liquid carbon dioxide product that will be exported by heat exchanger 12（Pressure is 15MPa）Being delivered to distance is
The place to use of 300km.
In gas-liquid separation tower 1,10,18 and 24, gas-liquid separation is carried out using gravitational settling method, the operating condition in tower is each
Identical from the condition of the entrance logistics with this device.Load activated carbon in removing oil tower 3, in desulfurizing tower 4, load zinc oxide, dehydrating tower
Molecular sieve is loaded in 5 and 6.Wherein, dehydrating tower 5 and dehydrating tower 6 are alternately in dewatering work pattern and reproduction operation pattern, every
Carry out material switching within 12 hours.
Temperature in removing oil tower 3 is 40 DEG C, and the temperature in desulfurizing tower 4 is 40 DEG C, and dehydrating tower 5 and 6 is in dewatering work mould
During formula, the temperature in tower is 40 DEG C；When being in reproduction operation pattern, the mean temperature in tower is 220 DEG C, in terms of gauge pressure, pressure
For 3.1MPa.
The specific process parameter of each step operation is listed in Table 1.The overall energy consumption of technique and the yield of liquid CO 2
List in table 2.It is assumed that the price of liquid CO 2 is 20 $/t, calculate technique gross investment and total revenue, result is in table 2
List.
Embodiment 2
Liquid CO 2 is produced using method same as Example 1, except for the difference that, liquid CO 2 conduct is used
Refrigerant.The specific process parameter of each step operation is listed in Table 1.The overall energy consumption of technique, the yield of liquid CO 2,
Technique gross investment and total revenue are listed in table 2.
Embodiment 3
Liquid CO 2 is produced using method same as Example 1, except for the difference that, not using the second gaseous stream as
Regenerating medium, but 8 moles of % in the CO 2 raw material gas stream that dehydrating tower 5 is exported are heated to after 230 DEG C, send into dehydration
It is used as regenerating medium in tower 6.Its concrete technology flow process is as shown in Figure 1.The specific process parameter of each step operation is listed in Table 1.
The overall energy consumption of technique, the yield of liquid CO 2, technique gross investment and total revenue are listed in table 2.
Comparative example 1
Liquid CO 2 is produced using method same as Example 3, except for the difference that, is not provided with choke valve 23 and gas-liquid
Knockout tower 24, the outlet pressure of compressor 2 is 2.5MPa, and its concrete technology flow process is as shown in Figure 3.The concrete technology of each step operation
Parameter is listed in Table 1.The overall energy consumption of technique, the yield of liquid CO 2, technique gross investment and total revenue arrange in table 2
Go out.
Embodiment 4
Liquid CO 2 is produced using method same as Example 1, except for the difference that, replaces choke valve using decompressor
23.The specific process parameter of each step operation is listed in Table 1.The overall energy consumption of technique, the yield of liquid CO 2, technique are total
Investment and total revenue are listed in table 2.
Table 1
Table 2
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Embodiment 4 |
| Power consumption (GJ (t CO2)) | 0.59 | 064 | 0.603 | 0.56 | 0.56 |
| Total consumption (t/ (t CO of recirculated water2)) | 17.6 | 18.00 | 17.8 | 17.81 | 16.08 |
| Total flow (t/ (the t CO of water vapour2)) | 0.0085 | 0.0092 | 0.0086 | 0.0066 | 0.0082 |
| Overall operation cost ($/(t CO2)) | 9.48 | 10.32 | 9.68 | 9.24 | 9.04 |
| Liquid CO2Yield | 0.86 | 0.871 | 0.86 | 0.712 | 0.889 |
| Gross investment * (1O4$) | 2765.97 | 2811.9 | 2815.8 | 2758.64 | - |
| Unit CO2Cost ($/(t CO2)) | 13.17 | 13.86 | 13.44 | 16 | - |
| Year total revenue (104$/a) | 176.21 | 160.44 | 169.34 | 85.44 | - |
*：Gross investment includes construction cost and operating cost, and wherein, construction cost accounts for the 30% of gross investment.
Can be seen that from the data of table 2 and be obtained in that using the method for the present invention liquid CO 2 significantly improving is received
Rate, such that it is able to effectively reduce the production cost of unit liquid carbon dioxide, is greatly improved total revenue.
Embodiment 1 and embodiment 2 are compared as can be seen that and liquid CO 2 is used as refrigerant phase
When liquefied ammonia is used as refrigerant, overall investment and operating cost are lower, the production cost of unit liquid carbon dioxide for ratio
Lower it is thus possible to obtain higher integral benefit.
Embodiment 1 and embodiment 3 are compared as can be seen that using the second gaseous stream as regenerating medium, Neng Goujin
One step reduces energy consumption and the production cost of the method for the present invention, thus improving integral benefit further.
Embodiment 5
Liquid CO 2 is produced using method same as Example 1, except for the difference that, is not provided with heat exchanger 21.
Gas in the power consumption of compressor 14, the recycling amount of refrigerant and the logistics after choke valve 22 expansion
Content is listed in table 3.
Table 3
Can be seen that to expand refrigerant from the data of table 3 sends into before liquefaction step, cold with refrigerant after heat exchange
But, can substantially reduce the gas content in refrigerant after expansion, improve the effective dose of the refrigerant sending into liquefaction step,
Thus reducing the circulating load of refrigerant, reduce the compression power consumption in refrigerant recycling step.
Embodiment 6
Liquid CO 2 is produced using method same as Example 1, except for the difference that, liquid propene is used as refrigeration
Medium.
The compression ratio of compressor 14, the recycling amount of refrigerant and total work done during compression are listed in table 4.
Table 4
Can be seen that from the data of table 4 and liquefied ammonia is used as refrigerant, and liquid propene is used as refrigerant phase
Than, can achieve identical liquefaction effect using lesser amount of liquefied ammonia, even if thus need higher compression ratio, made using liquefied ammonia
Remain able to reduce total compression power consumption for refrigerant.
Embodiment 7-10
Liquid CO 2, except for the difference that, the carbonated thing of use are produced using method same as Example 1
Carbon dioxide mean concentration in stream is different, and then the gas concentration lwevel in carbon dioxide feed stream is also different, titanium dioxide
Gas concentration lwevel in carbon raw material logistics is listed in table 5.
Power consumption in running and overall operation cost are listed in table 5.
Table 5
Can be seen that, from the data of table 5, the gas concentration lwevel improving CO 2 raw material gas stream, such as make carbon dioxide
Gas concentration lwevel in flow of feed gas is 85 moles of more than %, can substantially reduce the power consumption in running, reduces
Overall operation cost.
Embodiment 11
Liquid CO 2 is produced using method same as Example 1, except for the difference that, the concrete technology ginseng of each step operation
Number is listed in table 6.The overall energy consumption of technique, liquid CO 2 yield, technique gross investment and total revenue are listed in table 7.
Embodiment 12
Liquid CO 2 is produced using method same as Example 1, except for the difference that, the concrete technology ginseng of each step operation
Number is listed in table 6.The overall energy consumption of technique, liquid CO 2 yield, technique gross investment and total revenue are listed in table 7.
Embodiment 13
Liquid CO 2 is produced using method same as Example 1, except for the difference that, the concrete technology ginseng of each step operation
Number is listed in table 6.The overall energy consumption of technique, liquid CO 2 yield, technique gross investment and total revenue are listed in table 7.
Table 6
Table 7
| Project | Embodiment 1 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Power consumption（GJ/(t CO2)） | 0.59 | 0.58 | 0.56 | 0.53 |
| Total consumption of recirculated water（t/(t CO2)） | 17.6 | 16.6 | 16.0 | 15.3 |
| The total flow of water vapour（t/(t CO2)） | 0.0085 | 0.0075 | 0.0063 | 0.0057 |
| Overall operation cost（$/(t CO2)） | 9.48 | 9.45 | 9.36 | 9.32 |
| Liquid CO2Yield | 0.86 | 0.843 | 0.801 | 0.763 |
| Gross investment（104$） | 2766 | 2805 | 2851 | 2856 |
| Unit CO2Cost（$/(t CO2)） | 13.17 | 13.22 | 13.45 | 13.66 |
| Year total revenue（104$/a） | 176.21 | 171.47 | 157.40 | 145.12 |
The result of embodiment 13 shows, can significantly improve the yield of liquid CO 2 using the method for the present invention, from
And improve total revenue.By embodiment 1 with embodiment 11 is compared with embodiment 12 and embodiment 13 it can be seen that so that dioxy
The pressure of change carbon raw material air-flow is the critical pressure higher than carbon dioxide, is obtained in that higher liquid CO 2 yield, from
And obtain higher total revenue.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (31)
1. a kind of method producing liquid CO 2, the method includes expansion step, the first gas-liquid separation step, liquefaction step
And heat exchange steps：
In described expansion step, the CO 2 raw material gas stream of precooling is expanded, logistics after being expanded, described pre-
The pressure of the CO 2 raw material gas stream of cooling is to be not less than 4MPa；
In described first gas-liquid separation step, isolate not condensate logistics after described expansion, obtain the first gaseous stream
With first liquid carbon dioxide；
In described liquefaction step, the atmospheric carbon dioxide liquefaction in described first gaseous stream obtains titanium dioxide containing liquid
The logistics of carbon；
In described heat exchange steps, by CO 2 raw material gas stream and described first liquid carbon dioxide and/or in liquid
Change the logistics containing liquid CO 2 that obtains in step and carry out heat exchange, obtain described precooling CO 2 raw material gas stream and
Product liquid carbon dioxide.
2. method according to claim 1, wherein, the method also includes：Carry out the second gas after described liquefaction step
Liquid separating step, in described second gas-liquid separation step, isolates not condensate from the described logistics containing liquid CO 2,
Obtain the second gaseous stream and second liquid carbon dioxide, so that by CO 2 raw material gas in described heat exchange steps
Stream carries out heat exchange with described first liquid carbon dioxide and/or described second liquid carbon dioxide.
3. method according to claim 1 and 2, wherein, the method also includes：By titanium dioxide in described heat exchange steps
Carbon raw material air-flow and described first liquid carbon dioxide and/or the thing containing liquid CO 2 obtaining in liquefaction step
Before stream carries out heat exchange, carry out pre-treatment step, in described pre-treatment step, carbonated air-flow is pressurized, will increase
Air-flow after pressure carries out removing oil, desulfurization and/or dehydration, obtains described CO 2 raw material gas stream.
4. method according to claim 1 and 2, wherein, the pressure of described CO 2 raw material gas stream is 5-15MPa.
5. method according to claim 4, wherein, the pressure of described CO 2 raw material gas stream is to be not less than carbon dioxide
Critical pressure to 15MPa.
6. method according to claim 5, wherein, the pressure of described CO 2 raw material gas stream is higher than carbon dioxide
Critical pressure is to 15MPa.
7. method according to claim 6, wherein, the pressure of described CO 2 raw material gas stream is 8-12MPa.
8. method according to claim 3, wherein, the pressure of described CO 2 raw material gas stream is 5-15MPa.
9. method according to claim 8, wherein, the pressure of described CO 2 raw material gas stream is to be not less than carbon dioxide
Critical pressure to 15MPa.
10. method according to claim 9, wherein, the pressure of described CO 2 raw material gas stream is higher than carbon dioxide
Critical pressure to 15MPa.
11. methods according to claim 10, wherein, the pressure of described CO 2 raw material gas stream is 8-12MPa.
12. methods according to claim 1, wherein, the temperature of the CO 2 raw material gas stream of described precooling is -20 DEG C
To 20 DEG C.
13. methods according to any one of claim 1,2 and 12, wherein, dioxy in described CO 2 raw material gas stream
The content changing carbon is 70 moles of more than %.
14. methods according to claim 13, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is
85-95 mole of %.
15. methods according to claim 3, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is 70
Mole more than %.
16. methods according to claim 15, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is
85-95 mole of %.
17. methods according to claim 4, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is 70
Mole more than %.
18. methods according to claim 17, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is
85-95 mole of %.
19. methods according to claim 8, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is 70
Mole more than %.
20. methods according to claim 19, wherein, in described CO 2 raw material gas stream, the content of carbon dioxide is
85-95 mole of %.
21. methods according to claim 1, wherein, the expansion ratio in described expansion step is 1.5-8.
22. methods according to claim 21, wherein, the expansion ratio in described expansion step is 2-6.
23. methods according to claim 3, wherein, the method for described dehydration includes：Under dehydration conditions, after being pressurized
Air-flow contact with dehydrant.
24. methods according to claim 23, wherein, described dehydrant is molecular sieve.
25. methods according to claim 24, wherein, the method also includes regeneration step, in described regeneration step,
Under regeneration condition, the molecular sieve of inactivation is contacted with regenerating medium.
26. methods according to claim 25, wherein, at least partly described regenerating medium comes from described second gas gas-phase objects
Stream and/or a part of described CO 2 raw material gas stream.
27. methods according to claim 26, wherein, by described second gaseous stream send into described regeneration step before with institute
State the air-flow after supercharging and carry out heat exchange, to improve the temperature of described second gaseous stream.
28. methods according to claim 1, wherein, in described liquefaction step, by refrigerant and described first gas phase
Logistics heat exchange, the condition of described heat exchange makes the co 2 liquefaction in described first gaseous stream, obtains titanium dioxide containing liquid
Refrigerant after the logistics of carbon and heat exchange.
29. methods according to claim 28, wherein, described refrigerant is liquefied ammonia, liquid CO 2 and liquid third
One or more of alkene.
30. methods according to claim 29, wherein, described refrigerant is liquefied ammonia.
31. methods according to claim 29 or 30, wherein, the method also includes：Described refrigerant is sent into described
Carry out heat exchange with refrigerant after the heat exchange of described liquefaction step output, to reduce the temperature of described refrigerant before liquefaction step
Degree.
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Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy Research Institute Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: NATIONAL INSTITUTE OF CLEAN-AND-LOW-CARBON ENERGY |