CN101053737A - Novel coupling film separating method and device used in gas separation - Google Patents
Novel coupling film separating method and device used in gas separation Download PDFInfo
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- CN101053737A CN101053737A CN 200710010337 CN200710010337A CN101053737A CN 101053737 A CN101053737 A CN 101053737A CN 200710010337 CN200710010337 CN 200710010337 CN 200710010337 A CN200710010337 A CN 200710010337A CN 101053737 A CN101053737 A CN 101053737A
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Abstract
The invention relates to a method for gas separating, a device thereof and a novel coupled film separation method for gas separating. The material gas is separated through a plurality of separation units, the material gas of each separation unit is firstly contacted with the gas separation film of one side, the gas component forming ligand structure with carrier solution by the form of improving transfer is firstly dissolving and diffusing in the gas separation film contacted therewith, then forms ligand structure with the carrier solution to pass the thin carrier solution and contact with the gas separation film at the other side by the form of improving transfer, and desorbs at the infiltration side by dissolving and diffusing in the gas separation film; the gas component in the material gas which can not form ligand structure with carrier solution is firstly dissolving and diffusing in the gas separation film contacted therewith, then contacts with the gas separation film at the other side by the form of dissolving and diffusing in the thin carrier solution, and desorbs at the infiltration side by dissolving and diffusing in the gas separation film to arrive at the purpose for separating the material gas. The separation method of the invention can satisfy the demand for the gas high pressure separating, avoid plastic effect, prevent wetness and leak of the film, and maintain long-time stability.
Description
Technical field:
The present invention relates to gas separating method, also relate to gas fractionation unit in addition.
Background technology:
It is that very important processing method, particularly olefin/paraffin are separated in the chemical industry always in occupation of important status in the chemical industry that gas separates.Ethene and propylene especially in the petrochemical industry output rank first place and second industrial chemicals.The isolation technics of olefin/paraffin mainly comprises cryogenic rectification, transformation absorption, oil-poor absorption, extracting rectifying etc. at present, and the general selectivity of these processes is relatively poor, separation is low, energy consumption is high.The raw material of alkene production at present is mainly derived from crude oil (naphtha, diesel oil, propane etc.) and natural gas (ethane, propane etc.).Because olefin/paraffin has very close boiling point, the number of plates that the destilling tower needs that are used to separate are a large amount of and very high reflux ratio.Typical ethylene/ethane destilling tower comprises 80-150 piece column plate (Sundaram, K.M.; Shreehan, M.M.; Olszewski, E.F.; Ethylene.Kirk-Othmer Encyclopedia of Industrial Chemistry, 4
ThEdition.John Wiley ﹠amp; Sons, Inc.:New York, 1994, Vol.9, pp 877-915).For propylene, then need two rectifying columns with 125 blocks of column plates, reflux ratio is also up to 12 to 20 (Gerhartz, W., Ed.Ethylene, Ullman ' s Encyclopedia ofIndustrial Chemistry.5
ThEdition.VCH Verlagsgesellschaft:Weinheim, 1987, Vol.A10, pp45-93).USDOE was at survey report (Humphrey, J.L. in 1991; Seibert A.F.; Koort R.A.; Separation TechnologiesAdvances and Priorties, U.S.Department of Energy Report 1991.12920-1) shows in that annual to be used for the energy consumption that olefin/paraffin separates be 0.12 * 10
15(≈ 0.13 * 10 for BTU
15KJ).Equipment investment that it is huge and energy consumption have promoted the isolation technics at olefin/paraffin separation field exploitation high-efficiency and economic, improve separative efficiency to cut down the consumption of energy and cost.Separate with regard to olefin/paraffin, membrane separation technique is considered to a most attractive replacement process, and it has strong challenge and competitiveness.In recent years, olefin/paraffin membrane separating technology has obtained development rapidly, and this isolation technics also is the focus and the emphasis of present gas film separation field research.Because this research still is in the exploratory stage at present in the world, main exploration route mainly concentrates on gas separation membrane, carrier promotes to transmit research fields such as composite membrane and supported liquid membrane.
With regard to carrier-free gas separation membrane,, deliver and announced a large amount of research papers and patent documentation in the world because the time of research is longer.Richard W.Baker is at its article of delivering " REVIEWS:Future Directions of Membrane Gas Separation Technology ", Ind.Eng.Chem.Res., 41 (2002) 1393-1411, propose owing to unstripped gas in the operating process of reality is controlled at about 6-10bar usually, the olefin/paraffin separation system will cause the serious plasticizing effect of gas separation membrane, cause the reduction of separating property, seriously hindered the process of its industrial applications.
Supported liquid membrane is another research direction that olefin/paraffin separates.Supported liquid membrane has shown good separating property for the separation of olefin/paraffin under original state, but the stability of long-time running is to hinder the principal element of supported liquid membrane development.Owing to the continuous evaporation of aqueous solvent, influenced the stability of film, finally caused the hyposmosis performance of olefin component and lower olefin/paraffin selectivity.M.Termamoto etc. are at its article of delivering " Separation of Ethylene from Ethane bya flowing liquid membrane using sliver nitrate as a carrier " J.Membr.Sci., 45 (1989) 115-136, the promotion carrier solution is formed the flowing liquid membrane phases by two film formed passages of hydrophobic micropore, unstripped gas and purging desorption gas are separated.Concerning olefin/paraffin separated, the operation with high pressure that this process can't satisfy unstrpped gas (ethylene/ethane, propylene) required (6-10bar), can't overcome the wetting of microporous barrier that long-time running causes again and revealed.
Thereby utilizing and forming high selectivity that reversible pi complex realizes that olefin/paraffin separates between transition metal and the alkene is the main direction of studying of olefin/paraffin film separation process in recent years.Exist in the film can be with the transition metal carrier of alkene coordination the time, the transmission of alkene is because the participation of carrier is reinforced the influence that the transmittance process of alkane then is not subjected to carrier.Pinnau etc. are in its United States Patent (USP) U.S.Patent5670051 (1997), Ag
+Be embedded in and form so-called solid polymer dielectric film in the polymer film, but the relatively poor chemical stability of alkene carrier seriously hinders the process of industrialization of this separation process.Simultaneously, Nymeijer etc. points out Ag at its article Sep.Pur.Technol.37 that delivers (2004) 209.
+For micro-H
2Gas such as S and acetylene is comparatively responsive, comprises Ag
+The solid polymer dielectric film regenerative process also very the difficulty and complicated, these factors are present industrialization aspect urgent problems.
In sum, olefin/paraffin is separated, gas separation membrane, carrier promote to transmit technology paths such as composite membrane and supported liquid membrane and all exist serious industrialization bottleneck problem, have restricted the development of process of industrialization.
Summary of the invention:
The objective of the invention is to overcome the disappearance of above-mentioned separation process, a kind of novel coupled film separation method that gas separates that is used for is provided, both can satisfy the high pressure separation requirement of unstrpped gas, stop the plastic effect of separation process; Can prevent the wetting and leakage phenomenon of film again, keep long-term stability.Also provide its separator in addition, uniqueness simple in structure, applying flexible.
The technical scheme that the present invention is adopted for achieving the above object is: be used for the novel coupled film separation method that gas separates, unstrpped gas is separated through a plurality of separative elements, each separative element unstrpped gas at first contacts with the gas separation membrane of a side, can form gas component at first the gas separation membrane that with it contact in the dissolving diffusion of part with carrier solution by promoting to transmit, form ligand structure with carrier solution then and contact with the opposite side gas separation membrane by the thin layer carrier solution, be diffused in the per-meate side desorb by the dissolving in this gas separation membrane to promote the transmission form; Can not form the at first dissolving diffusion in the gas separation membrane that contacts with it of gas component of part in the unstripped gas with carrier solution, form with the dissolving diffusion contacts with the opposite side gas separation membrane in the thin layer carrier solution then, be diffused in the per-meate side desorb by the dissolving in this gas separation membrane, reach the purpose of separate raw materials gas.
Described gas separation membrane is meant that the diffusion barrier with fine and close separating layer (dense layer) that adopts divided gas flow carries out gas and separates, and comprises asymmetric gas separation membrane (asymmetric gas separationmembranes) and composite gas diffusion barrier (composite gas separation membranes).
The gas separation membrane of described employing is an asymmetric gas separation membrane cellulose acetate (celluloseacetates), cellulose derivative (cellulosic derivatives), celluloid (cellulose nitrates), ethyl cellulose (ethyl cellulose), polyamide (polyamides), polyimides (polyimides), polyester (polyester), Merlon (polycarbonates), Copolycarbonate (copolycarbonate ester), poly-(many) ether (polyether), polyether-ketone (polyetherketones), PEI (polyetherimides), polyether sulfone (polyethersulfones), polysulfones (polysulfones), Kynoar (polyvinylidene fluoride), polybenzimidazoles (polybenzimidazoles), polyacrylonitrile (polyacrylonitrile), polyvinyl alcohol (polyvinylalcohol), polyvinyl chloride (polyvinylchloride), poly-azo aromatic hydrocarbons (polyazoaromatics), polyphenylene oxide/polyphenylene oxygen/poly-2,6-dimethyl-1,4-phenylate (polyphenylene oxide)/poly (2,6-dimethylphenylene oxide), polyureas (polyureas), polyurethane (polyurethanes), polyhydrazide (polyhydrazi des), poly-azomethine/poly methylene imine (polyazomethines), poly-(contracting) aldehyde (resin) (polyacetals), the rare lonitrile copolymer of styrene-third (styrene-acrylonitrilecopolymers), bromo polyxylene ether (brominated poly (xylene oxide)), sulfonation polyxylene ether (sulfonated poly (xylene oxide)), four halogenated polycarbonates (tetrahalogen-substituted polycarbonates), four halo polyester (tetrahalogen-substituted polyesters), polyamide-imide (polyamideimides), polyester-imides (polyimide esters), polyethersulfone ketone (PPESK)/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) (poly (phthalazine ether sulfone ketone)), blend and modification between sulfonated polyether sulfone ketone (PPESK)/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) (sulfonatedpoly (phthalazine ether sulfone ketone)) etc. and the material.
The separating layer of the composite gas diffusion barrier of described employing is dimethyl silicone polymer (polydimethylsiloxane (PDMS)), polysiloxanes (polysiloxanes), silicon rubber (silicone rubbers), natural rubber (nature rubbers), ethane-propylene (diene) rubber (ethane-propene (diene) rubbers), butadiene-nitrile rubber (nitrile butadienerubbers), polyvinyl alcohol (polyvinylalcohol), polyoxygenated dimethylbenzene (polyphenyleneoxide), polyoxyethylene (polyethylene oxide), polyyne (polyacetylenes), poly-4-methylpentene (poly (4-methylpentene)), poly-trimethyl silicane propine poly (trimethylsilylpropyne), polyvinyl trimethyl silane poly (vinyltrimethylsilane), polyurethane (polyurethanes), poly(ether-urethane) (polyetherurethanes) PEU, polyether block amide (Polyether block amide), (per) fluoropolymer (perfluorinated polymer) etc.
Described carrier solution comprises Ag
+, Cu
+And Pt
2+Deng can forming reversible complexing ligand transition metal ions, or form the chemical constituent of reversible part with separated materials such as carbon dioxide, hydrogen sulfide with olefin component.
Ag in the described carrier solution
+Ylidene ligands comprises AgNO
3, AgCF
3CO
2, AgCF
3SO
3, AgClO
4, AgBF
4Deng.
Described carrier solution is full of carrier solution passage in the diffusion barrier, perhaps circulates with certain speed and forms extremely thin liquid film layer.
Described carrier fluid thicknesses of layers is 20-10000 μ m, is preferably 100-1000 μ m.
Described carrier solution liquid film flow velocity can freely be controlled, and is generally 0-10m/s, is preferably 0-1m/s, is preferably 0-0.1m/s.
Pressure in the described carrier solution thin electrolyte film is controlled at 0-100atm, can perhaps be below or above feed side pressure for normal pressure or feed side pressure, preferably is controlled between pressure ± 2 atmospheric pressure of feed side.
Described unstrpped gas, carrier solution stream or infiltration gas can adopt different and stream, cross-flow, and the flow regime of wrong mixing in basic separative element both sides with inner.
All can adopt 0-180 degree angle to flow between the two-phase arbitrarily in described unstrpped gas, carrier solution and the infiltration gas.
Describedly can be passed through the per-meate side vacuum desorption by the gas component of desorb, carrier gas purging or atmospheric operation separate.
Described gas separating method is used to separate olefin/paraffin gas, carbon dioxide or hydrogen sulfide separation and carries dense.
The separator that separation method of the present invention adopted is mainly separative element, and there is carrier solution in separative element by the passage that forms certain width between two gas separation membranes in the passage.
Place the thin layer carrier solution passage that certain thickness filter forms between described two gas separation membranes, carrier solution is filled in the space between gas separation membrane and the filter.
The periphery of described two gas separation membranes adopts resin, sheet frame or heat-sealing to be sealed to the gas separation membrane bag, has the interface channel of two carrier solutions and external communications simultaneously on the gas separation membrane bag at least.
The diffusion barrier with fine and close separating layer that described gas separation membrane adopts gas to separate comprises asymmetric gas separation membrane and composite gas diffusion barrier.
The gas separation membrane of described employing is asymmetric gas separation membrane cellulose acetate, cellulose derivative, celluloid, ethyl cellulose, polyamide, polyimides, polyester, Merlon, Copolycarbonate, poly-(many) ether, polyether-ketone, PEI, polyether sulfone, polysulfones, Kynoar, polybenzimidazoles, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, poly-azo aromatic hydrocarbons, polyphenylene oxide/polyphenylene oxygen/poly-2,6-dimethyl-1,4-phenylate, polyureas, polyurethane, polyhydrazide, poly-azomethine/poly methylene imine, poly-(contracting) aldehyde (resin), the rare lonitrile copolymer of styrene-third, bromo polyxylene ether, sulfonation polyxylene ether, four halogenated polycarbonates, four halo polyester, polyamide-imide, polyester-imides, polyethersulfone ketone (PPESK)/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone), blend and modification between sulfonated polyether sulfone ketone (PPESK)/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) etc. and the material.
The separating layer of the composite gas diffusion barrier of described employing is a dimethyl silicone polymer, polysiloxanes, silicon rubber, natural rubber, ethane-propylene (diene) rubber, butadiene-nitrile rubber, polyvinyl alcohol, polyoxygenated dimethylbenzene, polyoxyethylene, polyyne, poly-4-methylpentene, poly-trimethyl silicane propine, the polyvinyl trimethyl silane, polyurethane, poly(ether-urethane), polyether block amide, (per) fluoropolymer etc.
Described gas fractionation unit is that a plurality of separative elements are formed, the separative element stack makes plate and frame or rolling device, the periphery of adjacent separative element diffusion barrier adopts resin, sheet frame or heat-sealing to seal unstrpped gas passage and the infiltration gas passage that forms certain width, and the both sides of each separative element are adjacent unstrpped gas passage and infiltration gas passage.
Described gas fractionation unit is that a plurality of separative elements are formed, and separator exists two to link to each other, exist at least one to link to each other with infiltration gas passage between the separative element with the infiltration gas interface channel of external communications and exist two to link to each other with carrier solution in the separative element gas separation membrane with the carrier solution interface channel of external communications at least with the unstrpped gas interface channel of external communications and unstrpped gas passage between the separative element at least.
The unstrpped gas passage is parallel connection or series connection or connection in series-parallel mixing between described each separative element.
The infiltration gas passage is parallel connection or series connection or connection in series-parallel mixing between described each separative element.
Carrier solution passage in described each separative element is parallel connection or series connection or connection in series-parallel mixing.
Described carrier solution interface channel is equipped with circulating pump.
Term used in the present invention " alkene " (olefin) refers to contain the hydrocarbon of the two keys of unsaturated C=C, for example ethene, propylene, butylene etc.Term used in the present invention " alkane " (paraffin) is meant the hydrocarbon that each C-C key is all saturated, for example ethane, propane, butane etc.Term used in the present invention " carrier solution " (facilitated transport carrier) is meant transition metal salt solution or certain compound solution that can form reversible complexing with olefin gas component or carbon dioxide or hydrogen sulfide gas.Term used in the present invention " promotes to transmit " (carrier facilitatedtransport) and is meant that carrier forms reversible complexing ligand in gas component to be separated and the carrier solution, and the transmission of this gas component is quickened owing to the participation of carrier and strengthened.Term used in the present invention " gas separation membrane " (gas separation membrane) can be used for the film that contains the dense gas separating layer that gas separates.Term used in the present invention " and stream " refers to that (cocurrent) flow direction of two bursts of logistics is identical.Term used in the present invention " adverse current " (countercurrent) refers to that the flow direction of two bursts of logistics is opposite.Term used in the present invention " cross-flow " (crossflow) refers to that the flow direction of two bursts of logistics is vertical mutually.
By separation method of the present invention, the olefin gas component that can form reversible complexing with carrier solution in gas separation membrane transmittance process and its carry out integral body at the promotion transmittance process of carrier solution and the desorption process in gas separation membrane and be coupled.And other gas component can't be transmitted by the promotion of carrier solution and strengthen its permeance property owing to can not form the part coupling with the alkene carrier solution in transmittance process, thereby reaches the purpose of separating with concentrated olefin gas component.With regard to olefin/paraffin, can overcome the bottleneck problem in the present olefin/paraffin separation process: both can satisfy the high pressure separation requirement of unstrpped gas olefin/paraffin, stop the plastic effect of separation process; Can prevent the wetting and leakage phenomenon of film again, keep long-term stability.Certainly, this process also can be applied to form and promote the carbon dioxide or the hydrogen sulfide separation of transmitting and carry dense.
The plurality of separate unit forms separation process by parallel connection, series connection or connection in series-parallel in the present invention.Unstrpped gas adopts series connection and/or parallel way to enter the plurality of separate unit, discharges in the unstrpped gas outlet.Infiltration gas adopts series connection and/or parallel way to compile discharge in the infiltration gas outlet.Carrier solution adopts series connection and/or parallel way to enter the plurality of separate unit, carries out replenishing and renewal of carrier solution.Carrier solution circulates under certain pressure and speed by circulating pump, the pressure of carrier solution can be controlled arbitrarily, can under normal pressure, operate, also can be controlled at operation under the feed side pressure, can also be controlled at and be below or above operation under the feed side pressure, preferably be controlled between pressure ± 2 atmospheric pressure of feed side.Certainly the present invention not only is used for the separation of olefin/paraffin gas, also be used in other promote to transmit by ligand solution carry out gas separated, such as gas separation process such as carbon dioxide, hydrogen sulfide.
Description of drawings:
Fig. 1: gas separation unit structural representation.
Fig. 2: the gas separation unit structural representation that has filter.
Fig. 3: unstrpped gas, carrier solution stream and infiltration gas are on gas separation unit and the stream mode schematic diagram.
Fig. 4: the adverse current view between unstrpped gas and carrier solution stream and stream and both and the infiltration gas.
Fig. 5: the separator structural representation of a plurality of separative element stacks (unstrpped gas, carrier solution stream also flow on gas separation unit with infiltration gas, and is in parallel between the separative element).
Fig. 6: ((unstrpped gas also flows or adverse current with carrier solution stream and infiltration gas on gas separation unit the separator structural representation of a plurality of separative element stacks; Unstrpped gas is connection in series-parallel between separative element, and carrier solution stream and infiltration gas gas are in parallel between separative element).
Fig. 7: theoretical modeling ethene and ethane are at the permeance property figure by gas separation unit.
Fig. 8: theoretical modeling ethene and ethane are by the desired separated performance map of gas separation unit.
Fig. 9: gas separation unit is diffusion barrier bag constructions schematic diagram (having carrier solution turnover pipe).
Figure 10: gas separation unit is diffusion barrier bag constructions schematic diagram (the whole runner of diffusion barrier bag is imported and exported the interface channel as carrier solution).
Figure 11: gas separation unit is diffusion barrier bag constructions schematic diagram (carrier solution interface channel mouth is positioned on the sheet frame).
Figure 12: gas separation unit is diffusion barrier bag constructions schematic diagram (the carrier solution interface channel is in diffusion barrier bag the same side).
Figure 13: the separator structural representation of some gas separation unit stacks.
Figure 14: the separator structural representation of several gas film bag separative element stacks.
Figure 15: separation process figure (unstripped gas transmits with infiltration gas transmission in parallel, carrier solution series connection).
Figure 16: separation process figure (unstripped gas, infiltration gas, carrier solution transmission in parallel).
Figure 17: separation process figure (unstripped gas, infiltration gas and carrier solution all connect transmission).
Figure 18: separation process figure (unstripped gas transmits with the connection in series-parallel of infiltration gas, and the carrier solution series connection is transmitted)
The specific embodiment:
There is carrier solution in the separative element 1 that is used for the gas separation as described in Figure 1 by the passage 3 that forms certain width between two gas separation membrane 2a, the 2b in the passage.
Being used for as shown in Figure 2 placed the thin layer carrier solution passage 3 that certain thickness filter 3a forms between separative element 1, two gas separation membrane 2a, the 2b that gas separates, and carrier solution is filled in the space between gas separation membrane and the filter.
The separative element 1 that is used for the gas separation shown in Figure 3, place the thin layer carrier solution passage 3 that certain thickness filter 3a forms between two gas separation membrane 2a, the 2b, carrier solution is filled in the space between gas separation membrane and the filter, is stream mode also between unstrpped gas 4, carrier solution stream 5 and the infiltration gas 6.
Shown in Figure 4 be used for the separative element that gas separates, unstrpped gas 4 and carrier solution stream 5 and flow and both and infiltration gas 6 between the adverse current state.
Separator of the present invention comprises some gas separation unit (see figure 5)s, and unstrpped gas or infiltration gas passage are controlled by the distance of adjacent gas separation unit 1.The periphery of adjacent separative element adopts resin, sheet frame or heat-sealing to seal unstrpped gas passage 7 and the infiltration gas passage 8 that forms certain width, and the both sides of each separative element are adjacent unstrpped gas passage 7 and infiltration gas passage 8.Unstrpped gas 4 is by flowing in unstrpped gas passage 7, and by the transmittance process in the separative element 1 of sandwich structure, desorb separates in infiltration gas passage 8, and infiltration gas 6 compiles in the infiltration lane exit.There are two unstrpped gas interface channel 4a with external communications at least in separator, 4b links to each other, exists at least two the carrier solution interface channel 5a with external communications that link to each other with infiltration gas passage 8 with the infiltration gas interface channel 6a of external communications and exist at least with unstrpped gas passage 7,5b links to each other with carrier solution in the separative element.In the present invention, unstrpped gas 4, carrier solution stream 5 and infiltration gas 6 all can adopt in film separation unit and stream, adverse current, cross-flow and three's admixture.Unstrpped gas 4 can parallel different feed gas passages 7 (see figure 5)s that enter of parallel way.
Also can adopt grouping series system (see figure 6), unstripped gas 4 adopts the parallel feed gas passage 7 that enters of parallel way in each group film separation unit, two adjacent groups film resolution element adopts and is connected in series, and promptly goes up one group unstripped gas outlet and assembles the inlet that gas enters next group film resolution element.Each group film resolution element can comprise one to some feed gas passages.Infiltration gas 6 also can adopt parallel way (seeing Fig. 5, six) when flowing out separator; Also can adopt the grouping series system.Infiltration gas 6 also can adopt the type of flow of series system, parallel connection and connection in series-parallel combination when the turnover separator.The renewal of carrier solution in separator controlled by circulating of carrier solution with additional, and carrier solution stream also can adopt the type of flow of series, parallel and connection in series-parallel combination.Carrier solution flow velocity and pressure in the liquid film are controlled by the circulating pump 9 of outside, pressure is controlled at 0-100atm, can under normal pressure, operate, also can be controlled at operation under the feed side pressure, can also be controlled at and be below or above operation under the feed side pressure, preferably be controlled between pressure ± 2 atmospheric pressure of feed side.Can select in unstrpped gas passage 7 or the infiltration gas passage 8 to separate and support gas separation unit 1 with certain thickness filter.
Select for use PEI (PEI) perforated membrane as basement membrane, dimethyl silicone polymer (PDMS) is as the composite gas diffusion barrier of the compound separating layer material gas separation membrane as the gas separation membrane bag, and carrier solution is 4M AgNO in the gas separation membrane bag
3Solution.Do not consider the loss and the renewal of carrier solution during simulation, the flow velocity of carrier solution in the carrier solution passage is 0m/s.Unstrpped gas is pure ethylene and ethane.The separating property of composite gas diffusion barrier and ethene and ethane are at AgNO
3Physical characteristic in the carrier solution sees Table one.The thickness of carrier solution passage (d) is 300 μ m.Ethene carries out with dissolving diffusion form in the composite gas diffusion barrier, carries out with the form that promotes carrier transfer in carrier solution, is in poised state on film and carrier solution contact-making surface.Ethane carries out with dissolving diffusion form in the composite gas diffusion barrier, still to carry out with dissolving diffusion form, is in poised state on film and carrier solution contact-making surface in carrier solution.The feed side gas pressure is controlled at 100-2000kPa.The pressure of per-meate side is vacuum state.Analog temperature is 25 ℃.While is not considered the variation of the carrier solution concentration that the evaporation of carrier solution causes.Fig. 7 describes the influence of the variation of feed pressure to ethene and ethane permeability (Pressure-normalizedflux) theoretically.Fig. 8 has described the ideal separation factor (idealseparation factor) of ethene and ethane under different pressures.Here ideal separation factor is defined under the uniform pressure, the ratio of pure ethylene and ethane permeability.From Fig. 7 and eight and as can be seen, the ethene permeability can be controlled at 10-100 * 10
-6Cm
3/ cm
2.s.cmHg, the ideal separation factor of ethylene/ethane can meet the separation requirement of ethylene/ethane fully about 100 under the 500-1000kPa operating pressure.Also can be used for separating of other alkene and alkane in addition, select suitable species and carrier solution in the listed film of the present invention, also can be used for the separation of carbon dioxide, hydrogen sulfide.
In the present invention, the gas separation membrane bag is defined as basic separative element, forms the sandwich structure of gas separation membrane-carrier solution-gas separation membrane.Fig. 9 has described a kind of structural representation of basic gas separation membrane bag.At gas separation membrane 2a, form carrier solution passage between the 2b with certain thickness of thin layer (d), carrier solution stream 5 replenishes and renewal carrier solution so that certain speed is mobile in this passage.Between gas separation membrane, can place certain thickness filter 3a and support gas separation membrane.The thickness of while carrier solution is that the distance (d) between the gas separation membrane can be regulated by the thickness of filter 3a between the gas separation membrane.Carrier solution 3 is filled in gas separation membrane 2a, in the space between 2b and the filter 3a.For each gas separation membrane bag, carrier solution stream 5 with certain speed circulation, forms extremely thin liquid film layer in composite gas separates film formed passage.Thickness of liquid film is generally between the 20-10000 μ m, is preferably between the 100-1000 μ m.The liquid film flow velocity is generally between the 0-10m/s, is preferably between the 0-1m/s, is preferably between the 0-0.1m/s.Pressure in the liquid film is controlled at 0-100atm, can operate under normal pressure, also can be controlled at operation under the feed side pressure, can also be controlled at and be below or above operation under the feed side pressure, preferably is controlled between pressure ± 2 atmospheric pressure of feed side.In the process of operation, because the evaporation of solvent causes that the variation of carrier solution concentration can regulate by the circulation rate of carrier solution in the carrier solution.Film bag periphery 10a, 10b, 11a, 11b adopt resin, sheet frame to seal, and also can adopt heat-seal process to seal.Have at least two connector 12a simultaneously on the gas separation membrane bag, 12b is as the carrier solution and outside interface channel of gas separation membrane bag.By interface channel 12a, 12b reaches and replenishes and the purpose of upgrading carrier solution and control carrier solution pressure.
As Figure 10 the whole runner exit 11a of gas separation membrane bag 1,11b as and carrier solution and outside interface channel.
The gas separation membrane bag periphery of describing as Figure 11 adopts the sheet frame sealing.Interface channel 12a, 12b has been placed on the sheet frame, and carrier solution enters the carrier solution passage by the feeder connection 12a on the sheet frame, discharges by the channel outlet 12b on the sheet frame then, realizes replenishing and renewal of carrier solution.
Passing through connector 12a, 12b is placed on on one side as Figure 12.And changing the flow regime of carrier solution by the baffle plate 11c in the film bag, baffle plate 11c can adopt resin, sheet frame to seal.
Embodiment three separators
Some gas separation membrane bags can make plate and frame film separation unit or rolled film separative element by stack.Keep certain distance between the adjacent gas separation membrane bag, form unstrpped gas or infiltration gas passage.Figure 13 has illustrated the stack schematic diagram of the basic resolution element of film of preparation film separation unit.M gas separation membrane bag and M+1 gas separation membrane bag form unstrpped gas passage 7.Its spacing (df) can be regulated by filter or sheet frame.M+1 gas separation membrane bag and M+2 gas separation membrane bag form infiltration gas passage 8.Its spacing (dp) also can be regulated by filter or sheet frame.M+2 the basic resolution element of film and M+3 the basic resolution element of film form unstrpped gas passage 7.Unstrpped gas passage and infiltration gas passage alternately occur successively.The spacing of raw material gas passage (df) between the 0.1mm-50mm, is preferably between the 0.2-10mm usually among the present invention.The spacing of infiltration gas passage (dp) between 0.1mm-50mm, is preferably between the 0.2-10mm usually among the present invention.In the present invention, unstrpped gas 4, carrier solution stream 5 and infiltration gas 6 all can adopt in film separation unit and stream, adverse current, cross-flow and three's admixture.Certainly all can adopt certain angle (0-180 degree) to flow between the two-phase arbitrarily in unstrpped gas 4, carrier solution stream 5 and the infiltration gas 6 in the present invention.The peripheral slit of adjacent gas separation membrane bag is adopted sheet frame, resin or other method to seal and is formed so-called unstrpped gas passage 7 or infiltration gas passage 8, also can adopt heat-sealing to seal.Exist at least two tube connectors to form the interface channel of unstripped gas and film separation unit outside on the unstrpped gas passage.Exist at least one tube connector to form the interface channel of infiltration gas and film separation unit outside on the infiltration gas passage.
Figure 14 has described a kind of film separation unit schematic diagram, but does not constitute the qualification to the invention practical range.Gas separation membrane bag 1 superposes successively, and unstrpped gas or infiltration gas passage are controlled by adjacent gas separation membrane bag distance.Adjacent gas separation membrane bag periphery 13,14 adopts sheet frame, resin or other method to seal and forms so-called unstrpped gas passage 7 and infiltration gas passage 8 with spacing df and dp.Can select in the passage to separate and support gas separation membrane bag with certain thickness filter.Exist at least two connectors 15 to form the interface channel of unstripped gas and film separation unit outside on every group of unstrpped gas passage 7.Exist at least one connector 16 to form the interface channel of infiltration gas and film separation unit outside on every group of infiltration gas passage 8.Unstrpped gas 4, infiltration gas stream 5 can adopt in film separation unit with carrier solution 6 and stream, adverse current, cross-flow and three's admixture.Unstrpped gas is by flowing in unstrpped gas passage 7, and by the transmittance process in the diffusion barrier bag 1 of sandwich structure, desorb separates in infiltration gas passage 8, compiles in the infiltration lane exit.There are two unstrpped gas interface channel 4a with external communications at least in film separation unit, 4b links to each other, exists at least two the carrier solution interface channel 5a with external communications that link to each other with infiltration gas passage 8 with the infiltration gas interface channel 6a of external communications and exist at least with unstrpped gas passage 7,5b links to each other with carrier solution in the film bag 1.
Unstripped gas can adopt grouping series system (see figure 6).Infiltration gas and carrier solution also can adopt the grouping series system.
Embodiment four film separation process
Connected mode between the separative element can adopt parallel connection, combinations such as series connection and connection in series-parallel.Figure 15 has described unstripped gas and the in parallel transfer mode of infiltration gas in different separative elements.Unstripped gas 4 parallel entering in the different film separation units, the outlet at film separation unit compiles then.Infiltration gas 6 adopts parallel way to collect.Carrier solution stream 5 adopts series system in different film separation units, carrier solution circulates by different film separation units with speed at certain pressure by outer loop pump 9 next time.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.Carrier solution stream 5 also can adopt parallel way in different film separation units, as Figure 16, carrier solution replenishes and renewal by different film separation units by circulating pump 9 is parallel under certain pressure and speed.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.
Unstripped gas and infiltration the connect transfer mode of gas in three separative elements as shown in figure 17.Unstripped gas 4 enters in the different film separation units successively, and infiltration gas 6 adopts series system to collect.Unstripped gas 4 at first enters first separative element (separative element one), enters next separative element (separative element two), to the last a separative element by (separative element one) outlet.6 in gas of infiltration has last component, and (separative element three) enters a last separative element (separative element two) from the unit, up to first separative element (separative element one).Infiltration gas 6 also can have first separative element (separative element one) to enter next separative element, to the last a separative element earlier.Carrier solution stream 5 adopts series system in different film separation units, carrier solution circulates by different film separation units with speed at certain pressure by outer loop pump 9 next time.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.Carrier solution stream 5 different film separation units also can in the employing parallel way.Carrier solution circulates by different film separation units by outer loop pump 9 is parallel under certain pressure and speed.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.
Figure 18 has described unstripped gas and has permeated gas at the connection in series-parallel transfer mode of two components in the unit.Unstripped gas 4 is at first parallel to be entered in first group of film separation unit, enters second group of film separation unit after unstripped gas compiles.Infiltration gas 6 adopts parallel way to collect in second group of film separation unit, enters first group of film separation unit after compiling.Carrier solution stream 5 adopts series system in different film separation units, carrier solution circulates by different film separation units with speed at certain pressure by outer loop pump 9 next time.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.Carrier solution stream 5 in different film separation units also can in the employing parallel way.Carrier solution circulates by different film separation units by compressor 9 is parallel under certain pressure and speed.The loss of the carrier solution that causes owing to evaporation or other reason simultaneously can have surge tank 17 to carry out supply.
The separating property of table one film and the physical characteristic of carrier solution (25 ℃)
| Stalling characteristic standard flux (Pressure-normalized flux) C of composite gas diffusion barrier 2H 4：720×10 -6cm 3(STP)/cm 2.s.cmHg C 2H 6：600×10 -6cm 3(STP)/cm 2.s.cmHg |
| Carrier solution (4M AgNO 3) physical characteristic: AgNO 3Concentration C BT＝4mol.dm -3＝4*10 3mol.m 3 C 2H 4With C 2H 6At 4MAgNO 3Solubility property in the solution [1] C 2H 4∶H A＝0.0260molm -3kPa -1 C 2H 6∶H A’＝0.0198molm -3kPa -1 C 2H 4With C 2H 6At 4MAgNO 3Diffusion in the solution [1] C 2H 4[Ag-C 2H 4]∶DA＝6.92*10 -10m 2.s -1 C 2H 6∶DA’＝1.14*10 -9m 2.s -1The product of the equilibrium constant and solubility coefficient [1] KH A＝3.08×10 -3kPa -1 |
[1]M.Teramoto，N.Takeuchi，T.Maki，H.Matsuyama，Sep.Purif.Technol.，28(2002)117-124
Claims (29)
1, is used for the novel coupled film separation method that gas separates, it is characterized in that: unstrpped gas is separated through a plurality of separative elements, each separative element unstrpped gas at first contacts with the gas separation membrane of a side, can form gas component at first the gas separation membrane that with it contact in the dissolving diffusion of part with carrier solution by promoting to transmit, form ligand structure with carrier solution then and contact with the opposite side gas separation membrane by the thin layer carrier solution, be diffused in the per-meate side desorb by the dissolving in this gas separation membrane to promote the transmission form; Can not form the at first dissolving diffusion in the gas separation membrane that contacts with it of gas component of part in the unstripped gas with carrier solution, contact with the opposite side gas separation membrane in the form of carrier solution then with the dissolving diffusion, be diffused in the per-meate side desorb by the dissolving in this gas separation membrane, reach the purpose of separate raw materials gas.
2, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: gas separation membrane is meant that the diffusion barrier with fine and close separating layer that adopts divided gas flow carries out gas and separates, and comprises asymmetric gas separation membrane and composite gas diffusion barrier.
3, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: the gas separation membrane of employing is asymmetric gas separation membrane cellulose acetate, cellulose derivative, celluloid, ethyl cellulose, polyamide, polyimides, polyester, Merlon, Copolycarbonate, poly-(many) ether, polyether-ketone, PEI, polyether sulfone, polysulfones, Kynoar, polybenzimidazoles, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, poly-azo aromatic hydrocarbons, polyphenylene oxide/polyphenylene oxygen/gather 2,6-dimethyl-1,4-phenylate, polyureas, polyurethane, polyhydrazide, poly-azomethine/poly methylene imine, poly-(contracting) aldehyde (resin), the rare lonitrile copolymer of styrene-third, the bromo polyxylene ether, the sulfonation polyxylene ether, four halogenated polycarbonates, four halo polyester, polyamide-imide, polyester-imides, polyethersulfone ketone/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone), blend and modification between sulfonated polyether sulfone ketone/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) etc. and the material.
4, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: the composite gas diffusion barrier separating layer of employing is a dimethyl silicone polymer, polysiloxanes, silicon rubber, natural rubber, ethane-propylene (diene) rubber, butadiene-nitrile rubber, polyvinyl alcohol, polyoxygenated dimethylbenzene, polyoxyethylene, polyyne, poly-4-methylpentene, poly-trimethyl silicane propine, polyvinyl trimethyl silane, polyurethane, poly(ether-urethane), polyether block amide or (per) fluoropolymer etc.
5, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: carrier solution comprises Ag
+, Cu
+And Pt
2+Deng the transition metal ions that can form complexing ligand, or form the chemical constituent of reversible part with separated materials such as carbon dioxide, hydrogen sulfide with olefin component.
6, the novel coupled film separation method that is used for the gas separation according to claim 5 is characterized in that: Ag in the carrier solution
+Ylidene ligands comprises AgNO
3, AgCF
3CO
2, AgCF
3SO
3, AgClO
4, AgBF
4Deng.
7, the novel coupled film separation method that is used for the gas separation according to claim 1 is characterized in that: carrier solution is full of the interior carrier solution passage of diffusion barrier or circulates the extremely thin liquid film layer of formation with certain speed.
8, the novel coupled film separation method that is used for the gas separation according to claim 7, it is characterized in that: carrier solution liquid film layer thickness is 20-10000 μ m.
9, the novel coupled film separation method that is used for the gas separation according to claim 7, it is characterized in that: carrier solution liquid film layer thickness is 100-1000 μ m.
10, the novel coupled film separation method that is used for the gas separation according to claim 7, it is characterized in that: carrier solution liquid film flow velocity is 0-10m/s.
11, the novel coupled film separation method that is used for the gas separation according to claim 7, it is characterized in that: carrier solution liquid film flow velocity is 0-1m/s.
12, the novel coupled film separation method that is used for the gas separation according to claim 7, it is characterized in that: carrier solution liquid film flow velocity is 0-0.1m/s.
13, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: the pressure in the carrier solution thin electrolyte film is controlled at 0-100atm, can be normal pressure or feed side pressure, perhaps be below or above feed side pressure, preferably be controlled between pressure ± 2 atmospheric pressure of feed side.
14, according to claim 1ly be used for the novel coupled film separation method that gas separates, it is characterized in that: unstrpped gas, carrier solution stream or infiltration gas can adopt different and stream, cross-flow, and the flow regime of wrong mixing in basic separative element both sides with inner.
15, the novel coupled film separation method that is used for the gas separation according to claim 1 is characterized in that: all can adopt 0-180 degree angle to flow between the two-phase arbitrarily in unstrpped gas, carrier solution and the infiltration gas.
16, the novel coupled film separation method that is used for the gas separation according to claim 1, it is characterized in that: can be passed through the per-meate side vacuum desorption by the gas component of desorb, carrier gas purging or atmospheric operation separate.
17, the novel coupled film separation method that is used for the gas separation according to claim 1 is characterized in that: gas separating method is used to separate olefin/paraffin gas, carbon dioxide or hydrogen sulfide separation and carries dense.
18, be used for the separator of the novel coupled film separation method of gas separation, it is characterized in that: it is mainly separative element (1), and there is carrier solution (3) in separative element by the passage that forms certain width between two gas separation membranes (2a, 2b) in the passage.
19, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: place the thin layer carrier solution passage (3) that certain thickness filter (3a) forms between two gas separation membranes (2a, 2b), carrier solution is filled in the space between gas separation membrane and the filter.
20, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: the periphery of two gas separation membranes (2a, 2b) adopts resin, sheet frame or heat-sealing to be sealed to the gas separation membrane bag, has the interface channel (5a, 5b) of two carrier solutions and external communications simultaneously on the gas separation membrane bag at least.
21, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: the diffusion barrier with fine and close separating layer that gas separation membrane (2a, 2b) adopts gas to separate comprises asymmetric gas separation membrane and composite gas diffusion barrier.
22, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: gas separation membrane (2a, 2b) be asymmetric gas separation membrane cellulose acetate, cellulose derivative, celluloid, ethyl cellulose, polyamide, polyimides, polyester, Merlon, Copolycarbonate, poly-(many) ether, polyether-ketone, PEI, polyether sulfone, polysulfones, Kynoar, polybenzimidazoles, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, poly-azo aromatic hydrocarbons, polyphenylene oxide/polyphenylene oxygen/poly-2,6-dimethyl-1, the 4-phenylate, polyureas, polyurethane, polyhydrazide, poly-azomethine/poly methylene imine, poly-(contracting) aldehyde (resin), the rare lonitrile copolymer of styrene-third, the bromo polyxylene ether, the sulfonation polyxylene ether, four halogenated polycarbonates, four halo polyester, polyamide-imide, polyester-imides, polyethersulfone ketone/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone), the blend between sulfonated polyether sulfone ketone/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) and the material with change.
23, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: gas separation membrane (2a, 2b) is a composite gas diffusion barrier dimethyl silicone polymer, polysiloxanes, silicon rubber, natural rubber, ethane-propylene (diene) rubber, butadiene-nitrile rubber, polyvinyl alcohol, polyoxygenated dimethylbenzene, polyoxyethylene, polyyne, poly-4-methylpentene, poly-trimethyl silicane propine, polyvinyl trimethyl silane, polyurethane, poly(ether-urethane), polyether block amide or (per) fluoropolymer etc.
24, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: gas fractionation unit is that a plurality of separative elements (1) are formed, the separative element stack makes plate and frame or rolling device, the periphery of adjacent separative element diffusion barrier adopts resin, sheet frame or heat-sealing to seal unstrpped gas passage (7) and the infiltration gas passage (8) that forms certain width, and the both sides of each separative element are adjacent unstrpped gas passage and infiltration gas passage.
25, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: gas fractionation unit is that a plurality of separative elements (1) are formed, and separator exists two to link to each other, exist at least one to link to each other with infiltration gas passage (8) with the infiltration gas interface channel (6a) of external communications and exist two to link to each other with the interior carrier solution (3) of the carrier solution interface channel of external communications and separative element gas separation membrane at least with the unstrpped gas interface channel (4a, 4b) of external communications and unstrpped gas passage (7) at least.
26, the separator that is used for the novel coupled film separation method of gas separation according to claim 18 is characterized in that: unstrpped gas passage (7) is parallel connection or series connection or connection in series-parallel mixing between each separative element (1).
27, the separator that is used for the novel coupled film separation method of gas separation according to claim 18 is characterized in that: infiltration gas passage (8) is parallel connection or series connection or connection in series-parallel mixing between each separative element.
28, the separator that is used for the novel coupled film separation method of gas separation according to claim 18 is characterized in that: carrier solution interface channel (5a, 5b) is parallel connection or series connection or connection in series-parallel mixing in each separative element.
29, the separator that is used for the novel coupled film separation method of gas separation according to claim 18, it is characterized in that: carrier solution interface channel (5a, 5b) is equipped with circulating pump (17).
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| CA2040798A1 (en) * | 1990-05-25 | 1991-11-26 | Dean T. Tsou | Facilitated liquid membranes for olefin/paraffin gas separations and related process |
| US5082472A (en) * | 1990-11-05 | 1992-01-21 | Mallouk Robert S | Composite membrane for facilitated transport processes |
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