CN104379236A - Method and system for removing carbon dioxide from hydrocarbons - Google Patents
Method and system for removing carbon dioxide from hydrocarbons Download PDFInfo
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- CN104379236A CN104379236A CN201380033118.8A CN201380033118A CN104379236A CN 104379236 A CN104379236 A CN 104379236A CN 201380033118 A CN201380033118 A CN 201380033118A CN 104379236 A CN104379236 A CN 104379236A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The present disclosure relates to a method for removing carbon dioxide from hydrocarbons, the method comprising the steps of: (a) contacting a feed stream comprising hydrocarbons and carbon dioxide with one or more gas-separation membranes to produce a hydrocarbon-rich retentate gas stream and a permeate gas stream rich in carbon dioxide, the retentate gas stream containing less carbon dioxide relative to the feed stream; and (b) passing at least one of the retentate gas stream or the permeate gas stream through an absorption unit to produce a hydrocarbon-rich gas phase and a liquid absorbent phase containing said carbon dioxide. The present disclosure also relates to a system for doing the same.
Description
Technical field
The present invention relates to the method and system removing carbon dioxide from hydrocarbon stream.
Background
Natural gas is the important sources of the light-hydrocarbon fuel mainly comprising methane, and due to its availability and relatively easily extract and be used to more and more replace traditional fuel widely compared with the traditional fuel of refining from crude oil.But many natural gas reservoirs comprise such as carbon dioxide (CO
2) the impurity of quite high part.Some natural gas reservoirs can comprise the CO higher than 30%
2content, such as 50% to 60% and up to 70%-90%.Other impurity can comprise such as hydrogen sulfide (H
2s), nitrogen (N
2) and the compound of carbon monoxide (CO).But, in most of reservoir, CO
2the major impurity composition of the raw gas that usual formation is extracted.Therefore, can be effective to before the energy produces, need process raw gas to remove CO at natural gas
2.Therefore, there are many methods this area to remove CO from the thick hydrocarbon stream of such as natural gas
2.
A kind of known method relates to gas separating method, wherein makes raw gas flow through film.Because the gas with various component in natural gas is to be different from the speed permeable membrane of the infiltration rate of methane, therefore raw gas body stream is separated into methane-rich stream and impurity enriched stream.But, a shortcoming of this method be for separating of elementary driving force be the difference of the dividing potential drop of infiltration component in osmotic flow and retentate stream.Therefore, separative efficiency reduces in time, because less impurity remains in natural gas flow carries secretly.In addition, because some methane are considered to together with dopants penetration by film, methane production therefore may be had significantly to lose up to 20%.But another shortcoming of gas separation is to be separated such as CO in gaseous form
2impurity.Due to can not by such as CO
2and H
2the sour gas of S is directly disposed to environment, therefore needs to provide CO
2storage facility, it needs compression step with convert gaseous CO usually
2for the high pressure conditions for Optimum storage.This compression step needs a large amount of consumption energy and causes high energy ezpenditure and cost.
For removing CO from hydro carbons
2another known method be gas scrubbing, wherein make the suitable sorbent medium contact in the absorption tower of natural gas and such as packed bed tower.Usually, the amine absorbent of such as MEA (MEA), diethanol amine (DEA), methyl diethanolamine (MDEA), diisopropylamine (DIPA) is used, because they easily absorb such as CO
2sour gas.But one of shortcoming of gas scrubbing is that it needs the expensive amine absorbent of buying and it needs to be back to the poor amine stream of absorption tower for washing further by using high-temperature gas (such as, fluid) to be separated constant regeneration to regenerate recirculation.Regenerative process inevitably causes some amine lose and need regularly to fill amine absorbent.In addition, known absorbing tower produces such as liquid flooding, bubbles and the problem of carrying secretly and installation and maintenance is expensive.
Therefore, need badly and be provided for removing CO from hydro carbons
2method and system, it overcomes or at least improves above-mentioned disclosed shortcoming.Especially, the CO be provided for from comprising high concentration is needed badly
2feed stream produce and have and be not more than 10%, be preferably less than 5%, be more preferably less than method or the system of the product natural gas flow of the carbon dioxide of 3%, it overcomes or improves the shortcoming of above-mentioned proposition.
General introduction
In an aspect, provide the method for removing carbon dioxide from hydro carbons, said method comprising the steps of: the feed stream that (a) makes to comprise hydro carbons and carbon dioxide contacts the carbonated infiltration gas stream of retentate gas flow and richness to produce hydrocarbon enrichment with one or more gas separation membrane, comprise less carbon dioxide compared to feed stream retentate gas flow; (b) at least one seepage flow of excess gas flow or infiltration gas is made by absorption plant to produce the gas phase of hydrocarbon enrichment and to comprise the liquid-absorbant phase of described carbon dioxide.
Compared to hydro carbons, feed stream can comprise the CO of primary amount
2.In one embodiment, feed stream can comprise up to 95%CO
2.In another embodiment, feed stream can comprise at least about 80%CO
2.
Hydro carbons in feed stream can comprise light C
1-C
4hydro carbons, compared to the methane (CH of other light hydrocarbon primary amount
4).In one embodiment, feed stream can comprise about 30% hydro carbons, and wherein about 29% is CH
4and remain 1% for C
2-C
4hydro carbons.
Advantageously, in the disclosed methods, at least one is passed into absorption plant further by the effluent penetrant of gas separaion UF membrane or retentate stream, increases and remove CO from natural gas
2efficiency keep CH simultaneously
4gross production rate.
In an embodiment of disclosed method, make to be rich in CO
2and pressure and CH
4the infiltration gas stream that content is low contacts with liquid-absorbant.Directly mix to prevent two-phase by permeable membrane separation infiltration gas stream and liquid-absorbant.The CO that can will carry secretly in infiltration gas stream
2absorb and remove from infiltration gas to liquid-absorbant, cause the formation of the gas phase of low pressure, methane-rich.Advantageously, the gas phase of this low pressure, methane-rich can be used as daily gas and can be used for produce power on the spot.More advantageously, this absorption step can reclaim a large amount of during the separating step of upstream together with CO
2penetration is by the CH of gas separation membrane
4, increase CH in product stream thus
4gross production rate.
In the alternate embodiment of disclosed method, make the retentate gas flow of the methane-rich of high pressure and liquid-absorbant but not CO
2the infiltration gas stream contact of enrichment.An advantage of operation like this is that it allows to make the CH produced by infiltration
4the mode of minimization of loss operates UF membrane step.In the configuration, although the retentate gas obtained from gas separaion step comprises a large amount of CO
2, but the CO carried secretly can be effectively removed during absorption step subsequently
2.Such as, in one embodiment, the first UF membrane step can be single stage membrane separation, although wherein remove less CO from raw natural gas
2, but advantageously have the hydrocarbon of minimizing to lose due to its single stage configuration.Which increase total CH
4productive rate.In addition, because gas separaion efficiency is along with CO remaining in gas material
2concentration and reduce, therefore there is single-stage gas separating step also in order to optimization CO
2remove, because gas fractionation unit can be designed to less (minimizing unit carbon discharge capacity (footprint)) and use less energy (cost savings).
In another aspect, provide the system for removing carbon dioxide from hydro carbons, described system comprises: (a) one or more gas fractionation unit, configure it with the feed stream of receiving package hydrocarbon-containifirst and carbon dioxide, wherein configure gas fractionation unit with the carbonated infiltration gas stream of retentate gas flow and richness producing hydrocarbon enrichment; (b) one or more absorption plant, it is positioned at described gas fractionation unit downstream, configuration absorption plant to receive at least one of retentate gas flow or infiltration gas stream, and wherein configures absorption plant with the carbonated liquid-absorbant phase of the gas phase and bag that produce hydrocarbon enrichment.
Compared to hydro carbons, feed stream can comprise the CO of primary amount
2.In one embodiment, compared to hydro carbons, feed stream can comprise up to 95%CO
2.
Hydro carbons in feed stream can comprise light C
1-C
4hydro carbons, has the methane (CH of primary amount compared to other light hydrocarbons
4).
Advantageously, disclosed system connects gas fractionation unit and the membrane contactor device being positioned at downstream, and it significantly improves CH
4gross production rate and improve CO
2the efficiency removed.Of the present invention another favourable in, disclosed system provides design flexibility by configuration membrane contactor device to receive at least one and leave the osmotic flow effluent of gas fractionation unit or retentate stream effluent.As discussed with reference to said method, this flexibility allow the design of gas separaion with show single-stage or multistage configuration thus balancing run person to minimization system carbon discharge capacity, best CO
2remove and maximize CH simultaneously
4the requirement of productive rate.
Definition
Following word used herein and term should have the implication of regulation:
" the %CO used in the context of the present specification
2" refer to mol%, unless specified otherwise herein.
" " substantially " does not get rid of, and " " fully ", such as, " composition of " there is no " Y can be does not have Y to word completely.If desired, word " " substantially " can be omitted from definition of the present invention.
Unless specified otherwise herein, term " comprises (comprising) " and " comprising (comprise) " and grammatical variants intention representative " open " or " comprising formula " thereof are expressed the element that they comprised enumerate but also allow to comprise element that is other, that do not enumerate.
As used herein, in the context of formulation components concentration, term " about " typically refers to the +/-5% of setting, the more generally +/-4% of setting, the more generally +/-3% of setting, the more generally +/-2% of setting, the even more generally +/-1% of setting, and the +/-0.5% of even more generally setting.
In the disclosure, some embodiments can be disclosed range format.The description that should be appreciated that range format is object and the unmodifiable restriction that should not be interpreted as open scope for convenience and simplicity only.Therefore, the description of scope should be considered to have the independent numerical value in concrete disclosed all possible subrange and described scope.Such as, the description of the scope of such as 1 to 6 should be considered to have such as 1 to 3,1 to 4,1 to 5,2 to 4,2 to 6,3 to 6 etc. concrete disclosed subrange and described scope in independent numeral, such as, 1,2,3,4,5 and 6.No matter described range wide is much, and afore mentioned rules is all applicable.
Accompanying drawing is sketched
Accompanying drawing illustrates disclosed embodiment and principle in order to explain disclosed embodiment.But, be to be understood that design accompanying drawing only for illustrative purposes, and should not be interpreted as the definition of boundary of the present invention.
Fig. 1 is for representing the schematic diagram for the treatment of the simplification of flowsheet of the first embodiment of the system disclosed in natural gas.
Fig. 2 is the schematic diagram of the simplification of flowsheet of the second embodiment representing disclosed system, the penetrant wherein leaving membrane separator to membrane contactor but not retentate stream run.
Accompanying drawing describes in detail
With reference to figure 1, the exemplary of disclosed system 10 shown in simplification of flowsheet figure.
First methane gas (CH is comprised from natural gas pretreatment unit or direct transport from raw gas source
4) and the carbon dioxide (CO of major concentration (up to 95%)
2) raw gas raw material 12 and be under high pressure delivered to membrane separator device 14.Raw gas raw material 12 can be carried under the pressure of about 20 bar to about 70 bar.
Membrane separator device 14 comprise one or more with spiral winding collocation form arrangement diffusion barrier 46 thin slice or multiple with restraint collocation form arrange hollow-fibre membrane.Make the gas material 12 of high pressure by " shell " side of diffusion barrier 46.Due to compared to CH
4, CO
2more have permeability for film 46, therefore the retentate stream 28 of high pressure is formed and its CH in " shell " side
4concentration improve.On the contrary, " inner chamber " side of film forms the osmotic flow 32 of low pressure, its CO
2concentration improve.Osmotic flow 32 is in about 1 bar usually under the lower pressure of about 30 bar.In this stage, compared to raw gas raw material 12, the retentate stream 28 leaving membrane separator device 14 comprises less CO
2, and be generally about 20% to 40%.
The osmotic flow 32 of the low pressure leaving membrane separator device 14 can be made to be stored for optimization in storage device 38 again to pressurize by compressor 34.Or, osmotic flow 32 can be made by after-treatment device for CO
2isolation.
Subsequently, the retentate stream 28 of high pressure is made to flow to membrane contactor device 16.Membrane contactor device 16 comprises at least one film 44 arranged in contactor and it divides membrane contactor device to form at least one gas flow area and at least one liquid flow region.More than one film 44 can be provided in membrane contactor device 16, such as, multiple film 44 can be provided in hollow fiber bundle configuration.
Configuration membrane contactor device 16, to receive the liquid absorbent stream 22 entered, enters its liquid flow region.Select liquid absorbent stream 22 to be any liquid medium, its performance is to CO
2preferential affinity and it is not easy film 44 of getting wet.In one embodiment, liquid-absorbant 22 is seawater.But other liquid-absorbants are also expected in the scope of disclosed system, comprise the amine absorbent of such as MEA, MDEA and DEA.But current seawater is preferred, due to its availability and inappreciable cost.By pumping system 18, liquid absorbent stream 22 is transported to membrane contactor device 16.
Further configuration membrane contactor device 16 enters its gas flow area to receive retentate stream 28.In this embodiment, gas flow and liquid absorbent stream each other adverse current arrangement but cross-current and co-current flow configuration also in the scope of disclosed system 10.Usually, select hydrophobic microporous membrane such as but not limited to polypropylene (PP), polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF), polysulfones (PSf), polymine (PEI) film to form the permeable barrier between gas and liquid flow region.The aperture of film can be 0.01 μm to about 4 μm.In one embodiment, the aperture of selective membrane makes it can easily by CO
2molecule fills up to make maximize surface area for CO
2absorb the liquid-absorbant 22 entered.The CO carried secretly in retentate stream 28
2dissolve and enter contiguous liquid absorbent stream 22, formed and comprise high concentration CO
2effluent liquid stream 24.Effluent liquid stream 24 leave contactor arrangement 16 and be transferred into treating apparatus 26 for the treatment of/processing.
The effluent gas flow 42 leaving contactor arrangement 16 is rich in CH
4gases at high pressure and comprise CO that is a small amount of or negligible quantity
2.In one embodiment, effluent gas flow 42 comprises and is less than 10%, is preferably less than 5%, is even more preferably less than the CO of 3%
2.Suitably can change the CO in effluent gas flow 42
2concentration is to meet acid gas specification.
An advantage of this configuration is that single stage membrane separation can be used for membrane separator device 14.This makes overall hydrocarbon minimization of loss, because expect CH at least partially
4also film 46 is penetrated through to form a part of osmotic flow (although with than CO
2slower speed).By having single stage membrane separation device, CH can be made
4minimization of loss, balance is some CO
2still carry secretly in retentate stream 28.Advantageously, by junctional membrane separator and downstream contact apparatus 16, still can effectively remove the CO carried secretly
2effluent gas flow 42 is made to reach the CO of expectation
2concentration.In addition, because retentate stream 28 has experienced first by being separated, the absorption carrying capacity of membrane contactor device 16 has advantageously been reduced.Finally, by using seawater as liquid-absorbant, this is availability due to seawater and does not need further to install independent amine regenerating unit.Disclosed in another embodiment, system 10 is that height cost is effective, and liquid-absorbant can be distilled water.In another embodiment, liquid-absorbant can be and comprises to improve CO
2the water of the additive absorbed.
With reference now to Fig. 2, the alternate embodiment of the system 50 for the treatment of natural gas of the present invention is shown.In this embodiment, the raw gas raw material 52 of high pressure is made by membrane separation device 54 to form CH
4the retentate stream 56 of enrichment and CO
2the osmotic flow 58 of enrichment.In this embodiment, membrane separation device 54 can comprise multiple film module 84 and be suitably configured for Using Multistage Membranes gas separaion.Such as, arranged in series form can be arranged in the film module 84 arranged in membrane separation device 54 and make gas material 52 must experience two-stage or multi-level gas to be separated.Significantly, series connection and progression can be suitably selected to make retentate stream 56 comprise the CO of acceptable concentration
2with satisfied sale or consumption requirement.In one embodiment, the quantity of selective membrane module 84 makes retentate stream 56 comprise the CO being less than or equal to about 10%
2.By compressor 62 retentate stream 56 to be pressurizeed and with acid gas 64 direct marketing.
Owing to carrying out multi-stage separation in upstream, the CH of the major part (up to 15%) therefore in gas material 52
4may no longer belong to osmotic flow 58.Therefore, osmotic flow 58 still comprises the product hydrocarbon CH of primary amount
4.Therefore, after this osmotic flow 58 is delivered to membrane contactor device 86, configures it thus with counter-current flow to the contiguous liquid absorbent stream 72 separated by permeable membrane 82.Other flow arrangement of such as cross-current or co-current flow also can be used for membrane contactor device 86.Permeable membrane 82 divides membrane contactor device 86 to determine gas flow area and liquid flow region.Should be appreciated that and can provide more than one film 82 in absorption plant 86.Can one or more hollow fiber membrane bundle form or provide film 82 with the series connection arranged in absorption plant thin slice-form membrane.
Remaining CO in most of osmotic flow 58
2after being rapidly absorbed into liquid-absorbant 72, being formed and comprise a large amount of CH
4with the CO of low concentration
2the effluent gas flow 66 of low pressure.In one embodiment, effluent gas flow 66 comprises the CO being not more than 10%
2.Effluent gas flow 66 is generally about 1 to 30 bar.Advantageously, reclaim the CH of the permeation form in most of membrane separation device 54 with effluent gas flow 66 by membrane contactor device 86
4loss.In addition advantageously, effluent gas flow 66 directly can be used as daily gas with produce power on the spot, it reduces the external energy consumption of disclosure system.Be rich in CO
2liquid-absorbant leave membrane contactor device 86 as liquid efflunent stream 76 and can be directly delivered to holder 78 in the liquid phase.Or, liquid efflunent stream 76 can be made by the CO of after-treatment device for wherein comprising
2isolation.Advantageously, the CO absorbed of liquid form is in
2easy conveying and do not need expensive compression step to make CO
2be easy to store.
Disclosing of optional embodiment
Openly prepare now the exemplary non-limiting embodiments of the said method of the natural gas of first aspect.
In the disclosed methods, retentate gas flow or infiltration gas stream or the two can be made to carry out absorption step further to remove the CO comprised in those stream
2.In preferred embodiments, retentate gas flow is only made to carry out using the absorption of liquid-absorbant.In another embodiment, infiltration gas is only made to flow to the absorption of enforcement liquid-absorbant.
Contact procedure (a) also can comprise to be selected compared to CH
4to CO
2the step of the better gas-diffusion barrier of permeability.Can spiral winding configuration form or provide gas separation membrane with the form of the hollow fiber bundle arranged in membrane separator device.In one embodiment, gas separation membrane is made up of cellulose acetate.Other suitable gas separation membranes can be selected from the group including but not limited to polysulfones, polymine and polyamide/polyimide copolymer membrane.In another embodiment, gas separation membrane can be polyamide/polyimide copolymer membrane.The example of this kind of polyamide/polyimide copolymer membrane is commercially available
film.
Contact procedure (a) can comprise single-stage, twin-stage or multi-level gas separating step, wherein make raw natural gas body flow through gas separation membrane pipe side (or " inner chamber " side) and wherein at least partially raw natural gas body stream memory CO
2penetrant enters " shell " side to form low-pressure permeability gas flow or vice versa by film.In this aspect, the pressure of infiltration gas stream can be about 1 bar to about 30 bar.
When contact procedure (a) is for single stage membrane separation step, CO in retentate stream
2concentration can be about 20% to about 40%.When contact procedure (a) comprises twin-stage or Using Multistage Membranes is separated, the CO in retentate stream
2concentration can be about 20% to about 10%.In addition, the pressure of retentate stream can be about 20 bar to about 100 bar.The permeable membrane that theres is provided at least one to arrange in absorption plant can be comprised to determine at least one gas flow area and at least one liquid flow region by step (b).In one embodiment, absorption plant can be membrane contactor device.
Permeable membrane can by micropore and hydrophobic polymer material form substantially.The polymeric material of permeable membrane is optional from polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polymine, polyamide/polyimides, cellulose acetate or its copolymer.More than one film can be provided with spiral winding form, series connection sheet form or doughnut collocation form in absorption plant.Each film can be made up of identical or different polymeric material.Preferably, the film of selection should show high surface area and substantially compatiblely with liquid-absorbant should pollute with minimum membrane or soak.In one embodiment, permeable membrane is pvdf membrane.
Also can be comprised by step (b) makes any one gas flow area along absorption plant in retentate gas flow or infiltration gas stream pass through.The liquid flow region making liquid-absorbant along contiguous gas flow area also can be comprised, the CO comprised in retentate gas or infiltration gas during this period by step (b)
2liquid-absorbant is rapidly absorbed into by the hole of permeable membrane.In one embodiment, liquid absorbent stream and adjacent gas flow can pass through to produce CO between the two phases by countercurrent flow each other
2maximum partial pressure difference.Advantageously, the CO transmitting and enter liquid-absorbant is which increased
2quality.In another embodiment, relative to gas flow, liquid absorbent stream can and pass through to collocation form.
Also can be comprised by step (b) and provide and can absorb CO
2and it is to the step of the membrane material liquid-absorbant of inertia substantially.In one embodiment, liquid-absorbant is seawater.Advantageously, use seawater as liquid-absorbant due to its availability and inappreciable cost and widely on cost effectively.
In one embodiment, the retentate stream directly obtained from contact procedure (a) can comprise the CO being less than or equal to 10%
2, be preferably less than 5%, be even more preferably less than the CO of 3%
2.The CO being less than 10% is comprised at the retentate stream directly obtained from contact procedure (a)
2when, contact procedure (a) can comprise multi-level gas separating step.
In another embodiment, directly can comprise from the gas phase of the methane-rich obtained by step (b) CO being less than or equal to 10%
2, be preferably less than 5%, be even more preferably less than the CO of 3%
2.
In one embodiment, when making retentate gas flow carry out by step (b), the gas phase of methane-rich can be pressurizeed, there is the pressure of about 20 bar to about 100 bar.In another embodiment, when making infiltration gas flow to row by step (b), the gas phase of methane-rich can have the low pressure of about 1 bar to about 30 bar.
The open exemplary non-limiting embodiments for the preparation of the system of the natural gas of second aspect now.
In disclosed system, configurable absorption plant is to receive retentate gas flow or the infiltration gas stream that at least one leaves gas fractionation unit.In one embodiment, absorption plant can be provided in the downstream of both retentate gas flow and infiltration gas stream.In another embodiment, provide absorption plant only to receive retentate gas flow in downstream.In another embodiment, provide absorption plant only to receive infiltration gas stream in downstream.
In disclosed system, gas fractionation unit can comprise one or more film module be connected to each other with continuous or arranged in parallel or its combining form.Each film module can comprise the dense film arranged in one or more module arranging with the form of spiral winding or doughnut configuration.Each dense film can be made from the same material or a different material.Dense film can by permission CO
2compared to CH
4penetrate through the material composition of film sooner.In one embodiment, dense film is CAM.Other possible films are as discussed above.
Absorption plant can comprise one or more membrane contactor device.Each membrane contactor is included in the permeable membrane of setting in described contactor to determine the region of gas flowing and the adjacent area for liquid flow thus, wherein by permeable membrane separate gas flow region and liquid flow region.Configurable membrane contactor device leaves to receive retentate gas flow or the infiltration gas stream that gas fractionation unit enters gas flow area.Configurable membrane contactor device enters liquid flow region to receive liquid absorbent stream.In one embodiment, membrane contactor device is configured to make the liquid absorbent stream flowing of contiguous infiltration gas stream or retentate gas flow.In preferred embodiments, configure membrane contactor and make gas flow and liquid absorbent stream adverse current each other.In another embodiment, configuring membrane contactor makes gas flow and liquid absorbent stream be co-current flow form.
Permeable membrane in contactor arrangement can be essentially hydrophobic.In one embodiment, permeable membrane can be made up of micropore and hydrophobic polymer material substantially.The polymeric material of permeable membrane is optional from polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polymine or its copolymer.
In an embodiment of disclosed system, configuration gas fractionation unit comprises to produce the CO being less than or equal to 10%
2, be more preferably less than the CO of 5%
2, be even more preferably less than the CO of 3%
2retentate gas flow.In this embodiment, expect that separator comprises multiple film module arranged with hierarchical form and is separated to affect multi-level gas.In this embodiment, low-pressure permeability gas flow can be transported to one or more absorption plant to reclaim the gas phase leaving the methane-rich of the low pressure of absorption plant.The gas phase of the methane-rich of this low pressure can comprise the CO being less than or equal to 10%
2, be preferably less than 5% and be more preferably less than 3% CO
2.
In another embodiment, gas fractionation unit is configured to produce the CO comprising about 20% to 30%
2retentate gas.In this embodiment, retentate gas flow is made subsequently by one or more absorption plant to produce the gas phase of the methane-rich of high pressure.The gas phase of the methane-rich of this high pressure can comprise the CO being less than or equal to 10%
2, be preferably less than the CO of 5%
2and be more preferably less than the CO of 3%
2.In this embodiment, separator can only comprise single film module be configured for single-stage gas be separated.
Application
Above-mentioned disclosure provides from high CO
2cO is removed in concentration hydrocarbon stream
2effective, flexibly and cost effective method and system, overcome technical problem known in field simultaneously.Such as, the hydrocarbon that the combination of one or more gas fractionation unit and one or more downstream absorption device significantly reduces or cancels during separating step loses, and improves the CH of whole method and system thus
4productive rate.In addition, membrane contactor device is used to further avoid the known technical problem relevant with absorption tower as absorption plant because gas phase does not directly mix with liquid phase.
Even more advantageously, present disclose provides flexibly and the method and system that can customize, wherein can run described system to produce CO immediately after initial gas separation process
2the natural gas that content is significantly low, balance is during gas separaion, experience more hydrocarbon loss (but can be reclaimed by downstream absorption step).Alternatively, can operational system to make the hydrocarbon minimization of loss in initial gas separaion step, balance is more CO
2still carry secretly in retentate gas, be removed during its other absorption step in membrane contactor device.This flexibility certainly can be used for wherein space constraint and the energy and considers to affect the plant design of the operational mode selected for gas production system.
Significantly, to read after foregoing disclosure other amendments various of the present invention and reorganization under the spirit and scope of the invention be obvious for those skilled in the art and be intended to all such amendments and reorganization in the scope of accessory claim.
Claims (21)
1. from hydro carbons, remove the method for carbon dioxide, said method comprising the steps of:
A feed stream that () makes to comprise hydro carbons and carbon dioxide contacts the carbonated infiltration gas stream of retentate gas flow and richness to produce hydrocarbon enrichment with one or more gas separation membrane, compared to described feed stream, described retentate gas flow comprises less carbon dioxide; And
B () makes at least one of described retentate gas flow or described infiltration gas stream by absorption plant to produce the gas phase of hydrocarbon enrichment and to comprise the liquid-absorbant phase of described carbon dioxide.
2. the method for claim 1, wherein compared to described hydro carbons, described feed stream comprises the carbon dioxide of primary amount.
3. method as claimed in claim 2, wherein compared to described hydro carbons, described feed stream comprises up to 95%CO
2.
4. the method as described in claim arbitrary in aforementioned claim, wherein said being included in described absorption plant by step (b) provides permeable membrane to determine the gas flow area separated by described permeable membrane and liquid flow region thus.
5. method as claimed in claim 4, wherein said also being comprised by step (b) makes at least one of described retentate gas flow or described infiltration gas stream pass through along described gas flow area, the liquid absorbent stream that described gas flow area vicinity flows in described liquid flow region.
6. method as claimed in claim 5, wherein said also being comprised by step (b) is made the contiguous described retentate gas flow of described liquid-absorbant or described infiltration gas stream and flows, to enter described liquid-absorbant by least partially in the carbon dioxide absorption comprised in described gas flow.
7. method as claimed in claim 6, wherein said also being comprised by step (b) makes described liquid-absorbant and described retentate gas flow or described infiltration gas stream flow with counterflow configuration form.
8. the method as described in claim arbitrary in aforementioned claim, it also comprises selects compared to methane the better described gas separation membrane of carbon dioxide permeability.
9. from hydro carbons, remove the system of carbon dioxide, described system comprises:
A () one or more gas fractionation unit, configures it with the feed stream of receiving package hydrocarbon-containifirst and carbon dioxide, wherein configures described gas fractionation unit with the carbonated infiltration gas stream of retentate gas flow and richness producing hydrocarbon enrichment; With
(b) one or more absorption plant, it is positioned at described gas fractionation unit downstream, configure described absorption plant to receive at least one of described retentate gas flow or described infiltration gas stream, and wherein configure described absorption plant with the carbonated liquid-absorbant phase of the gas phase and bag that produce hydrocarbon enrichment.
10. system as claimed in claim 9, wherein said one or more absorption plant comprises one or more membrane contactor device.
11. systems as claimed in claim 10, wherein said membrane contactor device comprises at least one permeable membrane disposed therein, to determine the liquid flow region of being separated by described permeable membrane and gas flow area thus.
12. systems as claimed in claim 11, wherein configure described membrane contactor device to flow in described liquid flow region to make liquid absorbent stream, described liquid flow region adjacent passes through the described retentate gas flow of described flow region or described infiltration gas stream.
13. systems as claimed in claim 12, wherein configure described membrane contactor device and flow with counterflow configuration form to make described liquid-absorbant and described retentate gas flow or described infiltration gas stream.
14. systems as described in claim arbitrary in claim 11 to 13, wherein said permeable membrane is hydrophobic substantially.
15. systems as described in claim arbitrary in claim 9 to 14, wherein said liquid-absorbant is seawater.
16. systems as described in claim arbitrary in claim 9 to 15, wherein said gas fractionation unit comprises one or more dense film.
17. systems as claimed in claim 16, wherein said dense film arranges with the form of spiral winding or doughnut configuration.
18. systems as described in claim 16 or 17, wherein said dense film is compared to CH
4to CO
2permeability better.
19. systems as claimed in claim 18, wherein said dense film is made up of the material being selected from cellulose acetate, polysulfones, polymine, polyamide/polyimide copolymer and copolymer thereof.
20. systems as described in claim arbitrary in claim 9 to 19, the gas phase of the described retentate gas flow wherein leaving described gas fractionation unit or the described hydrocarbon enrichment leaving described absorption plant comprises the carbon dioxide being less than 10%.
21. systems as described in claim arbitrary in claim 9 to 20, the gas phase of the described retentate gas flow wherein leaving described gas fractionation unit or the described hydrocarbon enrichment leaving described absorption plant comprises the carbon dioxide being at least less than 5%.
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