CN1037462A - Water separating from hydrocarbon and halohydrocarbon - Google Patents
Water separating from hydrocarbon and halohydrocarbon Download PDFInfo
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- CN1037462A CN1037462A CN88108990A CN88108990A CN1037462A CN 1037462 A CN1037462 A CN 1037462A CN 88108990 A CN88108990 A CN 88108990A CN 88108990 A CN88108990 A CN 88108990A CN 1037462 A CN1037462 A CN 1037462A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
- B01D53/227—Multiple stage diffusion in parallel connexion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/268—Drying gases or vapours by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
- B01D63/046—Hollow fibre modules comprising multiple hollow fibre assemblies in separate housings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/081—Hollow fibre membranes characterised by the fibre diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/50—Specific extra tanks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- Water Supply & Treatment (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
A kind of in order to mixture from water and hydrocarbon, or the dried up device of branch in the mixture of water and halohydrocarbon, this device comprises the atresia of mainly being made by cuprous ammonium Mierocrystalline cellulose, the film with inside and outside surface that hollow fiber constituted that supports certainly, and the mixed flow in order to transmission hydrocarbon and water, make it the contacted piping of a side with film.Said film sucks water from mixed flow, make it to be penetrated into the opposite side of film, and then from this side of film water is removed.
Description
This paper is that application number is 108,752, the applying date is the part renewal application of the U.S. patent application case (now abandoning) on October 15th, 1987, is 880 and the latter is an application number, 783, the applying date is the part renewal application of the U.S. patent application case (now abandoning) on July 1st, 1986.
The present invention relates to a kind of dried up apparatus and method of from the mixture of water and hydro carbons, dividing.More particularly, the present invention relates to a kind of like this method, this method is used for removing the moisture of gas, and the water that is polluted by hydrocarbons is carried out decontamination.
Hydrocarbon from be present in chemical industry waste or contaminated with halogenated hydrocarbons thing or from hydrocarbon gas, divide dried up technology general requirement separation system can be exposed to the progress phase in the hydrocarbons and chemometamorphism or knot dirt (fouling) do not take place.Chemical degradation means that hydrocarbon or halohydrocarbon to the erosion of the chemical parts (as separatory membrane) in the tripping device, generally will cause the chemical degradation or the inefficacy of film system.Michaels will tie dirt and be described as a kind of like this phenomenon in " Utralfiltration Membranes and Applications; Polymer Science and Tcehnology; vol.13; 1979 ", whereby under normal operation, film presents the mobile resistance, has seriously limited and has worn film (transmembrane) infiltration capacity (concentration polarization).
Relating to isolating another the common situation of water one hydrocarbon is to separate the problem that the big or small much at one branch period of the day from 11 p.m. to 1 a.m is produced.For example, the size of water molecules is roughly identical with methane molecule.Therefore, the porous-film system with at present obtainable micropore can not divide boiling water and methane.Other film perhaps passes through chemically treated hydrophilic film, then because water by film pore hydrokinetics, still can make water and the methane pore by them.
Water vapor is the impurity in the industrial gas often, need during air-flow uses or handles or before be removed.For example, main ingredient is the Sweet natural gas of methane, contains the water of carrying secretly with physics mode of significant quantity under its native state.In many commercial runs, all wish and must carry out drying this class gas.
The method system of dry natural gas utilizes water at some material in the general prior art, and for example the solubleness in methyl alcohol or the ethylene glycol makes moist gas (hereinafter to be referred as moisture) achieve the goal with fluidic bath or fluid curtain (curtain) by washing.In these class methods, the washing that reaches capacity can be regenerated by driving away wherein moisture content with fluid, and the heat of discharging the gaseous combustion of (well-head) at first and producing is achieved the goal.The inherent cost is except comprising the cost that absorbs liquor itself in these class methods, in addition the expellant gas at first that is spent in water-saturated absorption liquor regenerative process.
In other prior art layout, be the employing adsorbent of molecular sieve, moisture is generally by being equipped with the bed of molecular sieve.Equally, the needs of Chuan regeneration or replacing will cause sizable energy consumption cost.
Use the solid adsorbent drying, and mechanical means operation (cooling or freezing is condensed to cause) is used also.
United States Patent (USP) 3,735,559(application people be Salemme, on May 29th, 1973 was announced) disclosed sulfonation poly-p-xylylene oxide film is used for separating water vapour from other gas.Said film is supported by supporting structure, and the latter has been interdicted the part surface of film.Smooth film is supported in two and supports between the web plate, forms a flat membrane module of interlayer.The problem of using this class film to be run into also has been discussed in this patent application document, as has been broken or the contraction of length.
United States Patent (USP) 4,421,529(application people be Revak etc., announce September 20 nineteen eighty-three) disclosed a kind of with the hollow-fiber film method of divided gas flow off and on.This patent discloses: hollow fiber can be made by various materials, comprises cellulose ester or ether of cellulose, is good with asymmetric rhodia especially wherein.This class film is a porous-film, from literal be to be used to filter hydrocarbon fluid.Owing to be porous, hydrocarbon can flow through these holes.In addition, the thickness of this class film is about 250 microns, and the thickness of film can produce adverse influence to the hydrokinetics of system.
As (author is S.Sourirajan to be entitled as " reverse osmosis a: frontier of applied chemistry and chemical engineering ", be the inventor of cellulose acetate membrane, this article is published in " Synthet ic Membrances ", vol.l, in 1981) disclosed in the literary composition, cellulose acetate membrane comprises asymmetric porous-film.This class porous-film is used for a kind of component in the solution on preferentially adsorbed film and the solution interface.There is no question about for this point, as as shown in the electron microscope (referring to Kesting, " Synthetic Polymeric Membrances ", 1971, the 40th page, Fig. 2 .17), the rhodia ultra-filtration membrane is a kind of cohesiveness system, it comprises and is called foamy opening (open), that is the vacuole that splits wall is arranged.Long side of body bar to three-dimensional extension tightens together cellulose net.
In the presence of halohydrocarbon, dissolving or degraded can take place in cellulose acetate membrane and ether of cellulose film.Hydrocarbons tends to make ether or the aceticoceptor generation chemical degradation that is exposed on the film surface in the hydrocarbon.
United States Patent (USP) 3,442,002(application people be Geary, Jr. etc., on May 6th, 1969 was announced) disclosed a kind of manufacture method of fluid seperation device, this device can comprise a plurality of separation assemblies.
United States Patent (USP) 2,981,680(application people is Binning, and on April 25th, 1961 was announced) disclosed a kind of method that is used to separate the molecular solution of the mixture that contains various ingredients, this method comprises uses two or more different (having different the composition) permeable membrane.This patent has disclosed the application of " regeneration " Mierocrystalline cellulose (300 PT type).300 PT fiber type elements are a kind of rhodias.Use the term of " regenerated cellulose " in this patent, meant the regenerated cellulose of chemical modification.On the meaning of strictness, " regenerated cellulose " speech typically refers to the Mierocrystalline cellulose without chemical modification, for example the Mierocrystalline cellulose that is produced by ammonium reclaiming process viscosity or cuprous.Roughly similar to natural cellulose by the Mierocrystalline cellulose that above back two kinds of methods regeneration obtains, from the regenerated cellulose that these methods produce, its chemical property does not change.
The change cellulose membrane (as rhodia) of (hereinafter to be referred as chemical modification) of chemical property is used to produce porous-film, and this normally a kind of asymmetric film is used for filtration process.This class chemical modification film have hydrocarbon (for example methane) in the presence of be easy to the degraded.
People's such as Skarstrom United States Patent (USP) 3,735,558 has disclosed a kind of method of separation of the fluid and used device thereof.This device is to produce a pressure gradient by the tube wall both sides at permeation tube, wears the wall infiltration to cause, water vapor is separated from air.Reflux will produce a radially concentration gradient at the tube wall along permeation tube, and the latter has strengthened the infiltration of main ingredient by tube wall, they can be separated from the mixed stream feed whereby.Both do not disclose the application of cuprous ammonium (cuproammonium) cellulose membrane in people's such as Skarstrom the patent, do not mentioned the problem of separate hydrocarbons from water yet.At last, people's such as Skarstrom patent has disclosed the application of semi-permeable membranaceous hollow film, and is different with no pore separation membrane, and this kind film is a porous.
Japanese Patent 13,653(1979 announced February 1) and 152,679(1979 announced December 1) all disclosed the method that water vapour is passed through with cuprous ammonium artificial silk.As above-mentioned other bibliographys, though also having disclosed cuprous ammonium cellulose membrane, this bibliography has the performance that to be passed through by water, expose but can tolerate in the mixture of hydrocarbon or halohydrocarbon and water continuously and for a long time, and the performance that the knot dirt of film or chemical property deterioration do not take place discloses or hints cuprous ammonium cellulose membrane.
The present invention relates to a kind of dispersion pattern film, this kind film can be made into the super thin fiber plate, like this, by providing fine passage to isolated water from hydrocarbon, will help hydrokinetics.The present invention also provides a kind of film that does not have supporting, and this film does not need to understand in addition the part surface of barrier film, and making it can not be directly and the contacted support of mobile hydrocarbon fluid.The present invention also provides a kind of energy the unexpected film that degraded takes place in hydrocarbon (for example methane) of resisting.Therefore, the invention provides a kind of apparatus and method that can from hydrocarbon fluid, divide dried up and dissolved water soluble ingredient very effectively.
Divide dried up device system to comprise that separate part, this part comprise the membrane assembly of mainly being made up of from the hollow cuprous ammonium cellulosic fibre of supporting atresia again from the mixture of water and hydrocarbon, said film comprises inside and outside surface.First piping is introduced the mixed flow of hydrocarbon and water, makes it to contact with a side of film.Film sucks water from mixed flow, and makes it the opposite side diffusion to film.Exclusive segment then removes the water of striping opposite side.
The present invention also provides a kind of dried up method of dividing from the mixture of water and hydrocarbon, this method comprises the following steps: the mixture of (1) introducing water and hydrocarbon, make it a side contacts with film, this film is mainly by having inside and outside surface, atresia, Zhi Cheng the cellulosic fiber of hollow cuprous ammonium constitutes certainly; (2) water penetrates in the film from mixture, and makes it to diffuse to the offside of film; (3) water of eliminating film second side; And (4) get rid of remaining mixture from first side of film.
With reference to hereinafter detailed description and relevant accompanying drawing, along with to further understanding of the present invention, other advantages of the present invention will be understanding easily.
Description of drawings:
Fig. 1 is the typical Pneumatic drying device side sectional view of the present invention;
Fig. 2 is a kind of part sectioned view of single fiber of form of the film that is used to make the present invention;
Fig. 3 is a partial view, shows in a kind of means, and the packaged type of the end of the film forming fiber of structure forms tube bank thus, and makes the opening end in fibrillar center hole or chamber become the passage of sweep air flow;
Fig. 4 is the amplification profile of the part-structure of film of the present invention;
Fig. 5 represents to use chamber (level) drying installation more than the present invention of this type film shown in Fig. 1 to Fig. 4; And
Fig. 6 is the synoptic diagram of third embodiment of the invention.
Below at length with reference to accompanying drawing, the wherein identical same parts of numbering system expression all are designated by numeral 10 at the strainer shown in Fig. 1.
Taking over 22 and 24 is near housing 12 respective end portions, and the fluid communication of participation and housing 12 inside.
The fibrous bundle 26 that hollow hydrophilic fibre 28 is formed extends axially in housing 12, forms the film that is commonly referred to as numbering 26.Fiber 28 is made up of regenerated cellulose, and its internal diameter (aperture) is preferably about 200 microns (± 10%).So-called regenerated cellulose is meant that used Mierocrystalline cellulose is cuprous ammonium regenerated cellulose.And cuprous ammonium regenerated cellulose is a kind of Mierocrystalline cellulose of deutero-non-chemically, is essentially native state.Cuprous ammonium regenerated cellulose is the cellulosic molecule layer on chemical structure.Its concrete ultrastructure is unknown, but has known already that it was soaked with the hole that penetrated layer.Thick hydrogen bond is arranged between layer, produce the structure of highly crystalline.This structure has suitable wetting ability, and provides aquaporin to the diffusion of water and dissolved water-soluble substances.The film that the made film of cuprous ammonium regenerated cellulose is made than the chemically derived filamentary material of rhodia and so on is much thin.Material by the diffusion of cuprous ammonium cellulose membrane the distance of process than distance much shorter by cellulose acetate membrane.In view of cuprous ammonium cellulose membrane can provide much smaller, but more efficiently barrier has only diffusion water and dissolved water-soluble substances to pass through to this, and therefore, cuprous amine cellulose film convection cell kinetics has tangible positive-effect.
Different with the asymmetry micropore cellulose acetate membrane of prior art, cuprous ammonium cellulose membrane of the present invention is a non-porous film.In the film of prior art, ether or acetate moiety group system are exposed in the surrounding medium of intersection, and cuprous ammonium tunica fibrosa is different with it, and the group of exposure is a hydroxyl, provides one deck to be difficult for by the non-degradable chemical layer of hydrocarbon or halohydrocarbon dissolving or decomposition thus.And, with former cuprous ammonium cellulose membrane in dry air or to be used for the applicable cases of water surrounding in medical dialysis equipment different, the inventor has found that, because the cellulosic chemical property of cuprous ammonium, in the presence of hydrocarbon, it can resist the chemical degradation effect out of a clear sky.The performance of this resistive connection dirt unexpectedly can be divided compound of the present invention continuously from water-hydrocarbon or water-Halocarbon blends under not having the dirty situation of knot dried up.
The United States Patent (USP) 4 of Christopher H.Porter and John ATaylor, 288,494(1981 announced September 8) and also be the United States Patent (USP) 4 of Porter and Taylor, 333,906(1982 announced June 8) in disclosed with cuprous ammonium Mierocrystalline cellulose and made the various technology that can be applied to hollow fiber of the present invention satisfactorily.Also can use this technical field skilled person can thinkable these class other technologies.
As required, can between film 26 and housing 12, screen 36 be set, so that film is firm, and structurally in advance with reinforcement, but the outside of single fiber does not add support.
Though device 10 provides two different fluid channels, respectively by housing 12.Especially as can be seen from the figure, enter the fluid of housing 12 along axially in housing 12, flowing by taking over 22, contact with the outside surface of fiber 28, and in this housing 12, axially flow to take over 24, a kind of transmission means that fluid from the hydrocarbon stream body source is contacted with the outer surface part of film are provided whereby.
The fluid that enters adapter 18 flows through centre hole 34 and chamber " C " of chamber " A ", fiber 28, flows out then and takes over 20, removes dry hydrocarbon fluidic storage equipment.
Referring now to Fig. 2, this is the sectional view (though wall thickness and not according to the ratio of reality) of single fiber 28.Fig. 2 is in order to the effect of fiber 28 skinnings 26 of explanation device 10, and from moisture dewatered mechanism.
For simplicity, in Fig. 2 with letter " W " expression moisture, as can be seen from the figure, enter take over 22 moisture along fiber 28(therefore along housing 12) the outer wall axial flow.Flow through the centre hole 34 of fiber 28 along direction with moisture " W " adverse current with the pressurized air gaseous purge stream of letter " S " expression.To keep a malleation gradient from outer wall 40 to its inwall 42 of the wall 38 of fiber 28.In other words, keep fiber 28 outer pressure (that is " B " indoor pressure) to surpass pressure in the centre hole 34, pass the wall of fiber 28, enter centre hole 34 with the material that helps to move.Certainly, any is arranged is clearly, although that is by making interior pressure (Pi) remain on a suitable high level, can keep a malleation gradient (Po is greater than Pi) effectively, the flattening of fiber 28 can be avoided.Pressure gradient can be from several pounds/inches
2To 1000 pounds/inch
2More than, as long as fiber is not crushed.Mass transfer efficiency rises along with pressure reduction and improves.
The fiber 28 of the film 26 in the shown device 10 is wetting abilities, do not have supporting, and diffusion water and dissolved water soluble ingredient are had preferential perviousness, and the gaseous medium (Sweet natural gas for example mainly is a methane) that carries moisture then can not see through.Because fiber is not have supporting, thereby fluid is continuously with unremitting at the mobile of fiber surface.Compare with the discontinuous film surface that supporting is arranged in the prior art, said structure causes the surface-area of fluid flow to increase, and helps the relative current body dynamics of system.Be adsorbed on the final wall that sees through fiber 28 that spreads of water on the fiber 28, arrive inwall 42.When water molecules appeared on the inwall 42 of fiber 28, mobile sweep air flow " S " was taken away water molecules immediately in center 34.The water that appears at like this on the inwall 42 is removed continuously by gaseous purge stream.Therefore, this film is a kind of proliferation part, mainly is made up of the nothing supporting with continuous free of discontinuities surface, the cuprous ammonium Mierocrystalline cellulose of atresia.Gaseous purge stream provides a kind of means that dewater, and promotes kinetics of diffusion, during hydrocarbon fluid passes through along fiber (all) length direction one way, can remove 95% water and dissolved water soluble ingredient at least from this fluid.Combine with ultra-thin cuprous ammonium fiber and as the scavenging stream of the means that dewater, and unobstructed continuous non-porous film surface provides the result of the separating dynamics that is greatly improved than the prior art system.These factors help device of the present invention during hydrocarbon fluid passes through along the staple length one way, can remove 95% water and dissolved water soluble ingredient from this fluid at least.
Comparatively it is desirable to, the fiber in the device 10 should be use up the thin of actual capabilities, because compare with thicker fiber, thinner fiber has higher resistance to pressure, and shows anti-flattening preferably.And, thinner, thereby a fairly large number of fiber provides higher fluid to transmit surface-area, therefore has higher efficient.
Fig. 4 represents to be positioned at the many fibers 28 of housing 12 numbers, and depicts the storage effect that each root fiber 28 moves in relevant mode among above-mentioned Fig. 2 significantly.
Referring now to Fig. 5, as can be seen from the figure, the system of general numbering 44 expressions is devices that are made of four assemblies, and wherein each assembly 46,52 is to install by reflux type.The moisture of taking over 54 accesss to plant 44 from the moisture feed flows through serial component 46,52 successively, then at dry gas (hereinafter to be referred as dry gas) quantity discharged 56 places, discharges and discharger as dry gas.The dry air gaseous purge stream enters menifold 58 at dry air inlet connection 60 places, concurrently by being arranged on each fiber (not shown) centre hole of the film in the assembly 46,52.The dry air gaseous purge stream enters menifold 62 by assembly 46,52 abreast, and then arrives wet discharged air downstream end 64.
Be applicable to that film of the present invention comprises the hydrophilic fibre film of Loeb and Sourirajan type, and at vol.2, " Synthetic Membranes Hyper-and Ultrafi ltration Use ", American Chemical Society Symposium Series 154, Albin F.Turbak, Editor(1981) this class film described in.Can use dialysis fiber type film.For different application, the rate of permeation of suitable film in fact can from zero until up to 20 ml waters/time mmhg rice
2
The 3rd embodiment of the present invention is shown in Fig. 6.This embodiment is specially adapted to water by hydrocarbon, the industrial application that fluorinated hydrocarbons or polychlorobiphenyl (PCB) pollute.
More particularly, this device comprises a filter assemblies according to manufacturing of the present invention, is provided with the Kong Ziwu that the cuprous ammonium Mierocrystalline cellulose of many regeneration makes in this assembly and holds hollow fiber.The mixture of the water 64 that is polluted by hydrocarbon (as oil) is housed in the storagetank 62, and this groove carries out fluid communication by the film outer surface in pipeline 66 and the housing 60.Pump 70 is added to the inlet tube 68 of positive pressure by housing 60 on the mixture in flowing.The water that diffuses through these hollow fibers is collected via gravity flowage, and leaves housing 60 by outlet pipe 72,74, flows into collection source (not shown) by pipeline 76,78 again.Be able to spissated mixture and leave housing 60 owing to water therefrom separates, and return retention tank 62 via pipeline 82 recirculation by pipeline 80.The continuous circulation of mixture is concentrated the mixture that is collected at first in the groove 62.Can other mixture be added in the groove 62 by pipeline 84 termly.Valve 86 can optionally be controlled fluid mixture and flow in the groove 62 by pipeline 84.
Second embodiment provides a kind of dried up method of dividing from water and hydrocarbon (or halohydrocarbon) mixture, this method comprises the steps: that (1) makes the outer side contacts of the mixture and the film of water and hydrocarbon, and said film comprises by cuprous ammonium Mierocrystalline cellulose and making, and the atresia with inside and outside surface is from supporting hollow fiber; (2) water infiltrates in the film from mixture; (3) water is to the offside diffusion of film.As mentioned above, water finally remove from second side of film, and remaining mixture is finally removed from first side of film by pipeline 82, returns storagetank 62 simultaneously by pipeline 76,78, to carry out recirculation and to concentrate.
Different with the device that uses film (for example cellulose acetate membrane) in the prior art is that the present invention can provide circulation over a long time to hydrocarbon contaminated water and concentrate, and can not tie dirt or deterioration.And the system of the sort of use cellulose acetate membrane can not separate contaminated water effectively from water-hydrocarbon mixture, also can not bear mix mace herd general ㄋ jealous woman of Chi T stand up Buddhist nunnery intelligence pavilion squid hold together the suitable stingy せ of Song Cuo Mount Tai ⑸ of to the quiet Meng of fried twisted dough sticks scandium war Yin a low S guanidine prolong the bits border high and steep of wise gown ether that walks lamely and finish the stingy さ of Song and receive that the squid is low gallops that the bright of arm convulsion ⒚ saddle cloth south is low really takes off the strange that leaps up to け ┞ to the slack green onion of the extensive nephew's cloud of show off clear ぞ smile institute and herd the mandrill Lu school dirty food badger neon of mounting and lead convulsion ⒚ evil spirit thatch Lv て and closely question torr ┞ and the cheat shortcake is unloaded to mandrill Lu encircle ⑸ to Suan
Embodiment 1
In the experimental installation 10 that uses this single assembly shown in a Fig. 1, film 26 comprises that effective surface area is 1 meter
2The cellulosic hollow fiber of the cuprous ammonia of regeneration.The working volume of film is 125 milliliters (0.125 liters).
Make moist methane gas by this device, contact with the film forming fiber outer wall of structure, the gaseous purge stream of drying nitrogen is the centre hole by fiber simultaneously then.
In once turning round, the temperature of moist methane is 80 ° of E, and dew point is 78 ° of E.The molar flow of methane (complete drying is a benchmark) is 4.1 * 10
-3Mole/minute, and the flow of water is 1.1 * 10
-4Mole/minute.The ingress nitrogen temperature is 79 °F, and dew point is-70 °F, and molar flow is 1.9 * 10
-2Mole/minute.The methane of separating device, its temperature are 74 °F, and dew point is 4.5 °F (though this water-content is lower than the lower limit that instrument is measured range).The discharge relevant with outlet methane is 6.7 * 10
-6Mole/minute, the gained result conservatively shows (because restriction of above-mentioned range of an instrument), 94% water is removed from methane.The temperature of discharging nitrogen is 74 °F, and 48 of dew points, the flow of water are 2.3 * 10
-4Mole/minute.After operation in 8 hours, above-mentioned running does not also reach stable state.
Embodiment 2
Yet in another time running, adopt much higher flow (more above-mentioned running is high 4 times), reach the stable state operation.In this running, after the operation in 30 hours, the dew point of discharging nitrogen reaches 22 °F ± 1 °F, after this keeps stable, and this shows that stable state reaches.The dew point of outlet is measured as 1.5 °F, illustrates that the water more than 95% is removed.
Above-mentioned example shows that this device 10 can be removed the water more than 95% from wet methane gas stream, and estimates to remove 99% water (under this experiment condition, being equivalent to-25 dew point approximately).On these results' basis, can think, use these apparatus and method ,-50 °F or more the dew point of low temperature finally can reach.
Embodiment 3
Making the water that is polluted by 3% heavy crude approximately flow through a surface-area is 2 meters
2The assembly of the plain hollow fiber of copper ammonia fibre.By the flows outside of the water of crude oil pollution at hollow fiber.Water spreads by the wall of hollow-fiber film immediately, simultaneously by means of gravity collection container of interior side inflow from hollow fiber.From be glass bright and clean and water white by the outward appearance of the water of separating the water of crude oil pollution, the water that pollutes then is Vandyke brown.By before the hollow-fiber film, measure by the concentration of the toluene in the water of crude oil pollution, dimethylbenzene and ethylbenzene.If use high-effect liquid chromatography technology, at detection limit is when analyzing under the 0.005ppm condition, the content of toluene, dimethylbenzene and ethylbenzene before separating is respectively 0.066ppm, and 0.263ppm and 0.062ppm then can not be detected in by the cleaning water of film.Carry out the running second time with same device, and the water sample pollutes with the zellon of 10ppm specially.The result who analyzes with high-effect liquid chromatography technology shows that the content that sees through zellon in the water of film can not be detected.
More than the example of Jie Shiing shows, the present invention can be effectively used to water is carried out decontamination, and makes it to get back in the environment under the situation of safety, and the method for finishing this process is a high-level efficiency and highly effective.
The present invention also provides a kind of method of anhydrating with the dissolved water soluble ingredient of removing from hydrocarbon fluid.Usually this method comprises the steps: to make hydrocarbon fluid stream one way to pass through, and meanwhile directly contacts with the length direction of the continual no area supported of the fiber of the cuprous ammonium cellulose membrane of some hollow atresias, and flows along this direction.When hydrocarbon fluid contacts with fiber, only there are water and the water miscible component of dissolved optionally to spread through this fiber in the hydrocarbon fluid.Dissolving is removed from the opposite side of film by the water and the dissolved water soluble ingredient of film, produces diffusion power, and remove 95% water and dissolved water soluble ingredient at least from hydrocarbon fluid.By remove water and the dissolved water soluble ingredient that diffuses through film continuously from fibrillar center, what keep thus that water and dissolved water soluble ingredient diffuse through film wears film (transmembrane) gradient.
Below by example the present invention is described, should be understood that the term that had used already only is used for explanation, and be not to limit the invention.
Obviously, according to above-mentioned technology, can carry out various conversion and change to the present invention.Therefore, should be understood that in the appending claims scope (numbering wherein for the purpose of the convenience, and be not to impose any restrictions), the present invention can also implement by the method outside the above concrete described mode.
Claims (24)
1, a kind of removing from hydrocarbon fluid anhydrated and the device of dissolved water soluble ingredient, and this device comprises:
(1) hydrocarbon stream body source;
(2) dry hydrocarbon fluidic storage equipment;
(3) a plurality of hollow-fiber films with inside and outside surface;
(4) transport unit, hydrocarbon fluid in order to transportation flow body source place, make it to contact with first surperficial length direction on said surface, and send into said storage equipment, said device is characterised in that said film comprises the diffusion part of mainly being made up of the cuprous ammonium Mierocrystalline cellulose of atresia that does not have supporting, it has the unremitting surface of successive, only can allow that the water-soluble component of water and dissolved diffuses out from hydrocarbon fluid, but also comprise water removal part, to produce diffusion power, during hydrocarbon fluid passes through along said staple length direction one way thus, can from hydrocarbon fluid, remove 95% water and dissolved water soluble ingredient at least.
2, device according to claim 1. it is characterized in that the mean thickness between the inside and outside surface of said each film is 9.5 to 10.5 microns.
3, device according to claim 2. it is characterized in that said water removal part comprises along the length direction mobile gaseous purge stream on second surface on said surface.
4, device according to claim 3. it is characterized in that said first surface is said outside surface, and said second surface is said internal surface.
5, a kind of removing from hydrocarbon fluid anhydrated and the method for dissolved water soluble ingredient, and this method mainly comprises the following steps:
(1) make the free of discontinuities of one hydrocarbon fluid, and do not have the length surface direction of supporting along the fiber of the cuprous ammonium cellulose membrane of some hollow atresias, and disposable the passing through of mode that directly contacts with it;
(2) when hydrocarbon fluid contacts with fiber, only there are water and dissolved water soluble ingredient in the hydrocarbon fluid optionally to spread through fiber; With
(3) remove water and the dissolved water soluble ingredient that diffuses through film from the opposite side of film, spread power to produce, and from hydrocarbon fluid, remove 95% water and dissolved water soluble ingredient at least.
6, method according to claim 5. it is characterized in that said water removes step and be further defined as the gaseous purge stream of introducing one and hydrocarbon fluid adverse current.
7, method according to claim 6. it is characterized in that said being further defined as by step makes the outside surface of this strand hydrocarbon fluid by fiber, and said water removes step and is further defined as to remove from internal surface and anhydrates and the dissolved water soluble ingredient.
8, method according to claim 7 is characterized in that said impregnation step is further defined as to make water and dissolved water soluble ingredient diffuse through one section mean distance from outside surface to internal surface only to be the distance of 9.5-10.5 micron.
9, from hydrocarbon fluid, remove anhydrate and the method for dissolved water soluble ingredient in, a side contacts of the permeable membrane of wherein initial wet hydrocarbon fluid and atresia, said step mainly comprises:
(1) tunica fibrosa of using the nothing supporting is as permeable membrane, and the material of said tunica fibrosa is selected from the group of mainly being made up of cuprous ammonium Mierocrystalline cellulose;
What (2) keep that water and dissolved water soluble ingredient diffuse through film wears film (transmembrane) gradient; With
(3) promote diffusion,, therefrom remove 95% water and dissolved water soluble ingredient with during the hydrocarbon fluid one way is by film.
10, a kind of method of using hollow-fiber film to come the hydrocarbon stream of dry wet, this method comprises the following steps:
(1) provide a kind of atresia that comprises, hollow, the film of hydrophilic cuprous ammonium regenerated cellulose fibre, this kind fiber can not be seen through by hydrocarbon;
(2) introduce moist hydrocarbon stream, make it and the outer side contacts of fiber, so that the water vapor in the air-flow sucked by fiber, and diffuse to the capable order of wash with watercolours
(3) introduce gaseous purge stream, make it by centre hole, with from centre hole and film, remove absorbed water and
(4) from film, remove dry gas.
11, method according to claim 10. the step that it is characterized in that said introducing gaseous purge stream means and becomes reverse mode to introduce basically with wet gas current gaseous purge stream.
12, method according to claim 11. the fiber that it is characterized in that said film is cuprous ammonium Mierocrystalline cellulose, and said wet gas current mainly comprises methane.
13, method according to claim 12. it is characterized in that film to the rate of permeation of water until 20 milliliters of/hour mmhg rice
2
14, in a kind of method with the moist hydrocarbon stream of hollow-fiber film drying, related step comprises:
(1) hollow fiber of the atresia made from cuprous ammonium Mierocrystalline cellulose, supporting certainly is as film;
(2) introduce moist hydrocarbon stream, make it to contact, so that the water in the air-flow sucked by fiber, and diffuse in the centre hole of fiber with the outside of fiber;
(3) from centre hole and film, remove the water that is inhaled into; With
(4) from film, remove dry gas.
15, method according to claim 14. it is characterized in that as the material of fiber to the rate of permeation of water can until reach 20 milliliters/time mmhg rice
2
16, method according to claim 15. it is characterized in that said wet gas current mainly comprises methane.
17, a kind ofly divide dried up device from water and hydrocarbon or Halocarbon blends, said device comprises:
(1) separate part, it comprises membrane element, and the hollow fiber of the atresia that said membrane element is mainly made by cuprous ammonium Mierocrystalline cellulose, supporting certainly constitutes, and said fiber comprises inside and outside surface;
(2) first translator unit is used to send into the mixture of hydrocarbon or halohydrocarbon and water, makes it the side contacts with said fiber, and said membrane element sucks water from said mixed flow, make it to be diffused into the opposite side of said fiber; With
(3) water is removed part, is used for removing from the opposite side of said fiber anhydrating.
18, device according to claim 17. it is characterized in that said water removes part and comprise second transfer member, remove from the opposite side of said membrane element by gravity flowage and anhydrate.
19, device according to claim 18. it is characterized in that said separate part comprises a housing, this housing is provided with (1) one in order to receive the mixture inlet pipe of mixture, one side of it and said membrane element has fluid communication, (2) water outlet pipes have fluid communication between second side of said membrane element and said second translator unit; (3) mixture outlet tubes have fluid communication with first side of said membrane element, and the inlet tube of this outlet pipe and said mixture is spaced a distance, to discharge mixture from said housing; Said device comprises recycling part, is with so that mixture is recycled in the mixture inlet pipe, and removes wherein moisture during first side by said membrane element at mixture at every turn, and mixture is concentrated continuously.
20, device according to claim 19. it is characterized in that said cyclic part comprises in order to hold and to store the bunkerage of quantity of recirculation mixture, said bunkerage comprises in order to receive other mixture, makes it to flow into the inlet tube of set bunkerage; And in order to optionally to control the valve part of received other mixture amounts.
21, a kind ofly divide dried up method from water and hydrocarbon or Halocarbon blends, this method comprises the following steps:
(1) introduce the mixture of water and hydrocarbon or halohydrocarbon, make it the side contacts with membrane module, and said membrane module comprises having the atresia of being made by cuprous ammonium Mierocrystalline cellulose on inside and outside surface, the hollow fiber that supports certainly.
(2) make water infiltrated fiber from mixture, and make it to be diffused into the offside of fiber;
(3) remove from second side of fiber and anhydrate; With
(4) remove remaining mixture from first side of fiber.
22, method according to claim 21. the wherein said step that dewaters is further characterized in that by means of gravity flowage except that anhydrating.
23, method according to claim 22. it is characterized in that this method also comprises the following steps:
(1) mixture of removing from first side of film makes it to be recycled to first side of film; With
(2) remove wherein moisture during at every turn by film at mixture, mixture is concentrated along with passing through each time.
24, method according to claim 23. it is characterized in that said recirculation step is further defined as:
(1) stores the mixture of removing from second side of film;
(2) added additionally mixed thing and the mixture of being stored are optionally merged; With
(3) optionally the mixture of being stored is sent into first side of film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US194,984 | 1988-05-11 | ||
| US07/194,984 US4857081A (en) | 1987-10-15 | 1988-05-17 | Separation of water from hydrocarbons and halogenated hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037462A true CN1037462A (en) | 1989-11-29 |
Family
ID=22719613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88108990A Pending CN1037462A (en) | 1988-05-11 | 1988-12-26 | Water separating from hydrocarbon and halohydrocarbon |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0217922A (en) |
| KR (1) | KR890016993A (en) |
| CN (1) | CN1037462A (en) |
| AU (1) | AU612192B2 (en) |
| IL (1) | IL87789A (en) |
| MY (1) | MY105085A (en) |
| NO (1) | NO884458L (en) |
| RU (1) | RU1819156C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103759998A (en) * | 2014-01-21 | 2014-04-30 | 北京汇丰隆生物科技发展有限公司 | Atmosphere dehumidification method and device |
| CN105688672A (en) * | 2014-11-26 | 2016-06-22 | 安徽智新生化有限公司 | Membrane dewatering device |
| CN108997079A (en) * | 2017-06-06 | 2018-12-14 | 中国石油化工股份有限公司 | A kind of dewatering of Benzene Chloride reaction solution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814087A (en) * | 1987-10-09 | 1989-03-21 | Separation Dynamics, Inc. | Fuel delivery system |
| US4790941A (en) * | 1988-03-18 | 1988-12-13 | Separation Dynamics, Inc. | Fluid decontamination system |
| JP2007330931A (en) * | 2006-06-16 | 2007-12-27 | Daiwa House Ind Co Ltd | Organic waste-treating method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2327106A1 (en) * | 1973-04-30 | 1974-11-21 | Charles William Skarstrom | METHOD AND DEVICE FOR SEPARATING INDIVIDUAL COMPONENTS FROM A FLOW MIXTURE |
| JPS5860010A (en) * | 1981-10-01 | 1983-04-09 | Asahi Chem Ind Co Ltd | Hollow fiber and dialytic membrane consisting of said hollow fiber |
| JPS62241527A (en) * | 1986-04-14 | 1987-10-22 | Daicel Chem Ind Ltd | Dehumidifying method for air |
| US4814087A (en) * | 1987-10-09 | 1989-03-21 | Separation Dynamics, Inc. | Fuel delivery system |
| US4790941A (en) * | 1988-03-18 | 1988-12-13 | Separation Dynamics, Inc. | Fluid decontamination system |
-
1988
- 1988-09-18 IL IL87789A patent/IL87789A/en unknown
- 1988-10-07 NO NO88884458A patent/NO884458L/en unknown
- 1988-11-07 AU AU24768/88A patent/AU612192B2/en not_active Ceased
- 1988-12-26 CN CN88108990A patent/CN1037462A/en active Pending
-
1989
- 1989-02-07 JP JP1028519A patent/JPH0217922A/en active Pending
- 1989-05-16 MY MYPI89000653A patent/MY105085A/en unknown
- 1989-05-16 RU SU894614000A patent/RU1819156C/en active
- 1989-05-17 KR KR1019890006570A patent/KR890016993A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103759998A (en) * | 2014-01-21 | 2014-04-30 | 北京汇丰隆生物科技发展有限公司 | Atmosphere dehumidification method and device |
| CN105688672A (en) * | 2014-11-26 | 2016-06-22 | 安徽智新生化有限公司 | Membrane dewatering device |
| CN108997079A (en) * | 2017-06-06 | 2018-12-14 | 中国石油化工股份有限公司 | A kind of dewatering of Benzene Chloride reaction solution |
Also Published As
| Publication number | Publication date |
|---|---|
| IL87789A0 (en) | 1989-03-31 |
| IL87789A (en) | 1992-05-25 |
| MY105085A (en) | 1994-08-30 |
| AU612192B2 (en) | 1991-07-04 |
| KR890016993A (en) | 1989-12-14 |
| RU1819156C (en) | 1993-05-30 |
| NO884458L (en) | 1989-11-20 |
| NO884458D0 (en) | 1988-10-07 |
| JPH0217922A (en) | 1990-01-22 |
| AU2476888A (en) | 1989-11-23 |
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