JPH0217922A - Apparatus and method separating water from hydrocarbon - Google Patents

Abstract

PURPOSE: To separate water and dissolved water-soluble components in high yield by bringing the hydrocarbon stream to contact with a hollow fiber membrane consisting of a nonporous cuproammonium cellulose. CONSTITUTION: A filter device 10 is constituted by arranging the membrane 26 bundling the nonporous hollow fiber 28 consisting of the cuproammonium regenerated cellulose in a housing 12. A wet hydrocarbon gas (for example, a natural gas consisting essentially of methane) is made to flow in from a port 22 and made to flow along an outer wall of the fiber 28. On the other hand, a sweep stream consisting of a dry air is made to flow in from the port 18 and discharged from the port 20 through an inside of the fiber 28. The water and the dissolved water-soluble component in the wet hydrocarbon gas are diffused through the membrane 26 and removed continuously by the sweep stream. A dry hydrocarbon gas is discharged from the port 24.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an apparatus and method for separating water from a mixture of water and hydrocarbons, and more particularly to a method for dehydrating gases and cleaning water contaminated with hydrocarbons. Concerning methods of removing contamination.

Separation of water from hydrocarbons, halogenated hydrocarbon contaminants found in chemical industrial wastes, or gaseous hydrocarbons generally requires long-term hydrocarbon removal without chemical deterioration or fouling. A separation device (system) that can be exposed to

Chemical degradation refers to the action of hydrocarbons or halogenated hydrocarbons on chemical components of separation equipment, such as separation membranes, and generally causes chemical degradation or failure of the membrane equipment. become.

Michaels, “Ultrafiltration membranes and their applications (Ultrafiltration membranes and their applications)”
tra-filtration) Iesbrane
s and Applications) J,
“Polymer Science and Technology (Polymer-
er 5science and Technology
) J (Vol, 13.1979) describes fouling as a phenomenon in which under normal operating conditions the membrane develops flow resistance and the membrane permeation flow rate is severely restricted (centralized decentralization).

Another common aspect regarding the separation of water and hydrocarbons is the problem caused by the separation of molecules of similar size.

For example, the size of a water molecule is approximately the same as the size of a methane molecule. Therefore, even the currently available porous membrane devices with the smallest porosity cannot distinguish between water and methane. Even with other membranes, that is, membranes that have been chemically treated to make them hydrophilic,
flow dynamics of water through the micropores of a membrane
cs) allows water and methane to pass through the micropores of these membranes.

Water vapor is often found in industrial gas streams and needs to be removed before or while the gas stream is used or treated. For example, natural gas (
In its natural state, methane, the main component of which is methane, contains large amounts of physically trapped water. In many industrial processes it is desirable or required that such gases be dried.

A conventional method of drying natural gas is to take advantage of the solubility of water in substances such as methanol or glycols by passing the moist gas through a bath or curtain of scrubbing fluid. In this method, when the scrubbing fluid becomes saturated with water, the scrubbing fluid is typically regenerated by evaporating the water using heat obtained from burning wellhead gas. This method thus inherently requires the cost of the sorption fluid itself, as well as the cost of the wellhead gas used to regenerate the water-saturated sorption fluid.

Other prior art arrangements include the use of molecular sieve adsorbents, where the moist gas is generally passed through a bed forming the molecular sieve. However, even this method requires considerable energy costs for refurbishing or replacing the bed.

Additionally, drying methods using solid adsorbents and mechanical manipulation (cooling or freezing to produce precipitation) have also been used.

U.S. Pat. No. 3,735,559 discloses sulfonated polyxylene oxide membranes for separating water vapor from other gases. The membrane is supported by a support structure that provides an obstruction to a portion of the membrane surface. A flat membrane is supported between two base screens to form a sandwich-shaped flat membrane assembly. The patent also discusses various problems encountered with membranes, such as membrane rupture and linear shrinkage.

U.S. Pat. No. 4,421,529 discloses a method for separating gases using spaced hollow fiber membranes. The patent also discloses that the hollow fibers can be made of a variety of materials including cellulose esters or cellulose ethers, preferably asymmetric cellulose acetate. These fibrous membranes are porous membranes that can truly filter hydrocarbon fluids. Because the membrane is porous, hydrocarbons can flow through the micropores. Furthermore,
These membranes have a thickness of approximately 250μ, which has a negative effect on the flow dynamics of the device.

S, 5o, the first person to use cellulose acetate membrane
Urirajan's writings [Reverse Osmosis, New Fields of Applied Chemistry and Chemical Engineering (Reverse Os+mossis:
A New Field of Applied Che
Mistry and Chemical Il! ng
ineering) J (magazine “Synthetic membrane (Synthet)
ic Membranes) J, Vol, 1.19
81), cellulose acetate membranes are composed of irregularly porous films. Such porous films are used to preferentially absorb one of the components of the solution at the interface of the film. Written by Kesting [
Synthetic polymer membrane (Synthetic P.

1yn+eric Membranes)J (197
1, p. 40, Fig. 2.17), ultrafiltration membranes made of cellulose acetate are flocculation devices consisting of open cells, or voids with broken walls. It is. What connects the cell network to each other is
It is a long rib extending in three dimensions.

In the presence of halogenated hydrocarbons, cellulose acetate and cellulose ethers dissolve or decompose.

Hydrocarbons have a tendency to chemically degrade the ether or acetate groups exposed to the hydrocarbon from the surface of the membrane.

US Pat. No. 3,442,002 discloses a fluid separation device with multiple separator modules.

U.S. Pat. No. 2,981,680 discloses a method for separating molecular solutions consisting of mixtures of components using two or more dissimilar (having different compositions) permeable membranes. There is. This US patent also discloses the use of "regenerated" cellulose (300PT type). 300 PT type cellulose is cellulose acetate.

As used in this U.S. patent, the term "regenerated cellulose" refers to [chemically modified reconstituted cellulose (
chemically modified recons
It means "tilted cellulose" J. Usually, the term "regenerated cellulose" has a stricter meaning and refers to chemically unmodified cellulose produced by the viscous regeneration process or the copper ammonium (cupra) regeneration process. These two
Cellulose regenerated by these regeneration methods is substantially the same as natural cellulose and is not chemically altered.

Chemically modified cellulose membranes such as cellulose acetate are used in the production of porous membranes (asymmetric membranes are usually used in the filtration process). These chemically altered membranes are susceptible to deterioration in the presence of hydrocarbons such as methane.

U.S. Pat. No. 3,735,558 discloses a fluid separation method and an apparatus used to carry out the fluid separation method. The fluid separation device is configured to allow permeation through the wall of the permeable tube to create a pressure gradient across the wall to separate water vapor from air.

The reverse reflux creates a longitudinal concentration gradient along the wall of the permeable tube, which enhances the permeability of important components through the tube wall, thereby transferring these components to the feed mixture. Can be separated from the fluid. This US patent does not disclose the use of cuprammonium cellulose membranes, nor does it discuss problems in separating hydrocarbons from water. The patent also discloses the use of semi-permeable hollow membranes, which are porous membranes as opposed to non-porous separation membranes.

Japanese Special Publication No. 13, 1979 (February 1, 1979)
(Issued on 1979) and Special Publication No. 152.679 (1979)
(Published December 1, 2013) discloses the use of cuprammonium rayon to selectively transmit water vapor.

Both of these publications, as well as the aforementioned U.S. patents, disclose the water permeability of cuprammonium cellulose membranes, but it is clear that copper ammonia There is no disclosure of the ability of cellulose membranes to withstand continuous and prolonged exposure to mixtures of hydrocarbons or halogenated hydrocarbons and water.

The present invention relates to a membrane of the diffusion type which can be made as an ultra-thin fiber membrane, ie a membrane which can actively contribute to the flow dynamics by allowing the water separated from the hydrocarbons to flow in the shortest possible time. Furthermore, the present invention provides an unsupported structure that does not require any additional support that would cover a portion of the membrane and prevent direct contact with the flowing hydrocarbon fluid. ) membrane is provided. Furthermore, the present invention provides membranes that have unexpectedly high resistance to degradation even in the presence of hydrocarbons such as methane. Accordingly, the present invention provides an apparatus and method for separating water and dissolved water-soluble components from hydrocarbon fluids with very high efficiency.

A device for separating water from a mixture of water and hydrocarbons or a mixture of water and halogenated hydrocarbons according to the invention comprises a membrane means formed of non-porous free-standing hollow fibers made of cuprammoniac cellulose. the membrane means having an inner surface and an outer surface. Also,
A first conduit means is adapted to introduce the hydrocarbon and water mixture to one side of the membrane means into contact therewith. The membrane means absorbs water from the mixture stream and diffuses it to the other side of the membrane means. Further, the removal means is configured to remove water from the other side of the membrane means.

Also in accordance with the invention, in a method for separating water from a mixture of water and hydrocarbons, a method for separating water from a mixture of water and hydrocarbons is provided, in which the method comprises a method for separating water from a mixture of water and hydrocarbons. introducing a mixture of water and a hydrocarbon into contact with one side of the membrane; absorbing water from the mixture into the membrane and diffusing water to the opposite side of the membrane; A method for separating water from a mixture of water and hydrocarbons, comprising the steps of: removing water from the opposite side of the membrane; and removing residual mixture from the one side of the membrane. is provided.

Other advantages of the invention will become apparent from the following detailed description of embodiments of the invention, taken in conjunction with the accompanying drawings.

In FIG. 1, the entire filter device is designated by the number IO. The same elements (components) are used throughout all drawings.
uses the same number.

Filter device 10 includes a shell or housing 12, which is illustrated as having a generally elongated cylindrical shape. Caps 14.16 are provided at both ends of the housing 12, and these caps 14.
A boat 18,20 is arranged axially in each of the boats 16.

Ports 22 are located adjacent opposite ends of housing 12 in fluid communication with the interior of housing 12.
．． 24 are provided.

Within the housing 12, a bundle of hydrophilic hollow fibers 28 extends in the axial direction of the housing, forming a membrane generally designated by the numeral 26. The fibrous membrane 28 is made of regenerated cellulose and preferably has an inner diameter (bore diameter) of about 200μ (±10%). The term regenerated cellulose means that the cellulose used in the present invention is cupro or cuprammonium regenerated cellulose. Cuprammonium regenerated cellulose is cellulose in its substantially natural state and not chemically derived. Cuprammonium regenerated cellulose is a chemical sheet consisting of cellulose molecules. Although the specific ultrastructure of the sheet is not known, it is known that the sheet has no micropores passing through it (non-porous). There are deuterium bonds between the sheets, creating a highly crystalline structure. This crystalline structure is completely hydrophilic and forms water channels through which water and dissolved water-soluble materials can diffuse. Cuprammonium regenerated cellulose is a warmer and thinner membrane than membranes made with chemically derived cellulose materials such as cellulose acetate. The distance traveled by a substance diffusing through a cuprammonium cellulose membrane is i smaller than the distance traveled by a substance migrating through cellulose acetate. Cuprammonium cellulose membranes therefore have a very positive influence on flow dynamics by forming a very small but effective barrier through which only diffusing water and dissolved water-soluble components can pass.

Irregular microporous membrane (as3nsetric m1cropo)
Unlike conventional cellulose acetate, which is a non-porous membrane, the cuprammonium cellulose membrane of the present invention is non-porous. Unlike conventional membranes that expose ether groups or acetate groups to the adjacent external environment, cuprammonium cellulose membranes that expose hydroxyl groups are easily dissolved or degraded by hydrocarbons or halogenated hydrocarbons. It forms a non-degrading chemical layer that will never be degraded. Also, unlike traditional methods of using cuprammonium cellulose membranes for air drying or medical dialysis equipment, in which cuprammonium cellulose membranes are used in humid environments, we We have discovered that cuprammonium cellulose has unexpected properties due to its chemical properties and is not chemically degraded in the presence of hydrocarbons. This resistance to contamination gives the present invention the unexpected ability to continuously separate water from mixtures of water and hydrocarbons or from mixtures of water and halogenated hydrocarbons without incurring contamination. I made it.

A technique for producing hollow fibers from cuprammoniac cellulose that is satisfactory for use in the present invention is disclosed in U.S. Pat.
, 288.494 and 4.333.906. Hollow fibers can be manufactured by other methods, if any, that can occur to those skilled in the art.

The interior of the housing 12 has spaced apart walls 30, 32 in sealing engagement with the inner wall surface of the housing 12, the housings 3o, 32 connecting the interior of the housing 12 to the end chambers A, C. and a central chamber B. The walls 3o, 32 surround and retain each end of the fiber 28, but leave the bore 34 of the fiber 28 open, as shown in FIG. 1 (and more particularly in FIGS. 3 and 4). and is placed in fluid communication with the end chambers A,C.

If desired, a screen 36 can be provided between the membrane 26 and the housing 12 to stabilize and structurally reinforce the membrane 26, but to prevent the individual fibers from being externally supported.

It will be seen that the filter device 10 is formed with two separate flow paths through the housing 12. In particular, the fluid flowing into the housing 12 from the port 22
to flow axially through the interior of the housing 12 towards the port 24 in contact with the outer surface of the fibers 28, thereby directing hydrocarbon fluid from the source in longitudinal contact with the outer surface of the membrane 26; An introduction means is formed. on the other hand,
Fluid entering from port 18 flows through end chamber A, bore 34 of fiber 28, and end chamber C, and then exits through port 20 to a storage location for dry hydrocarbon fluid.

In FIG. 2, a single hollow fiber 28 is shown in cross section, but the wall thickness is not drawn to scale. FIG. 2 is intended to explain the mechanism by which the fibers 28 of the filter device 1° function as a membrane 26 for removing moisture from humid gas.

Moist gas (conveniently designated W in FIG. 2) entering from port 22 flows along the outer wall of fiber 28 in the axial direction of fiber 28 (and thus of housing 12). Sweep flow consisting of compressed air
S is passed through the bore 34 of the fiber 28 as a counterflow to the flow direction of the wet gas W.

A positive pressure gradient is maintained across the wall 38 of the fiber 28 from the outer wall 40 to the inner wall 42 of the fiber 28 . In other words, the pressure Po outside the fiber 28 (i.e. the pressure inside the central chamber B) is
4 is maintained greater than the pressure PA within the fiber 28
This allows flow into the bore 34 across the wall 38 of the bore. Even when maintaining a positive pressure gradient (p, > p,), by maintaining the pressure P in the bore 34 at a moderately high pressure level, fibers 28 can be avoided from being crushed. As long as the fibers 28 are not crushed, the pressure gradient can be varied from a few psi to 1,000 psi (approximately 70 kg/
cm”) or higher.

The higher the pressure, the higher the efficiency of fluid passage.

The fibers 28 constituting the membrane 26 used in the illustrated filter device 10 are hydrophilic and arranged in an unsupported structure, allowing diffused water and dissolved water-soluble components to selectively permeate, while water The gaseous medium (e.g. methane-based natural gas) in which it is trapped is impermeable. fiber 2
8 is placed in an unsupported structure, the fluid flows through the fibers 2
can flow continuously unhindered over the surface of 8. The relative fluid dynamics of the device are improved by the greater surface area of the membrane exposed to fluid flow in the present invention compared to the prior art where the fibers are supported and the surface of the membrane is disturbed.
ics). Water absorbed by the fibers 28 will eventually diffuse through the walls 38 of the fibers 28 to the inner walls 42. The sweeping flow S of air flowing within the bore 34 carries away water molecules as they appear on the inner walls 42 of the fibers 28. The water appearing on the inner wall 42 is continuously removed by the sweeping flow. Membrane 26 is thus a diffusion means consisting of a substantially unsupported, non-porous copper ammonia cellulose with an unobstructed continuous surface. The sweep flow utilizes diffusion dynamism to remove at least 95% of water and dissolved water-soluble components from the hydrocarbon fluid while the hydrocarbon fluid is passed through the length of the fiber in one pass or round. forming a water removal means for removing %. When compared to the prior art, the sweeping flow acting as the water removal means, combined with the ultrathin cuprammonium cellulose and the undisturbed non-porous continuous membrane surface, improves the separation dynamics.
yields significantly improved results. These factors ensure that the filter apparatus 10 of the present invention removes at least 95% of the water and dissolved water-soluble components from the hydrocarbon fluid during a single pass of the fluid through the length of the cellulose 28.
It contributes to the ability of

The smaller the diameter of the fibers 28, the greater their pressure resistance and the greater their resistance to crushing (squeezing) than the larger diameter fibers; use something Also, the smaller the diameter, the more fibers can be used, increasing the surface area through which the fluid passes, and thus increasing efficiency.

FIG. 4 shows a number of fibers 28 associated with housing 12, visually illustrating the cumulative effect of the actions of individual fibers 28, as discussed above with respect to FIG.

FIG. 5 shows the individual modules 46.48.50.52
A four-module device assembly (indicated generally by numeral 44) is shown assembled in counterflow mode. Moist gas entering the four module device 44 from the moist gas source boat 54 is transferred to the four module device 46 .
52 in series and is exhausted as dry gas from the dry gas exhaust port 56. A sweeping stream of dry air enters manifold 58 from dry air inlet boat 60 and flows in parallel through bores in respective fibers (not shown) of membranes located within each module 46-52. A sweep stream of dry air flows in parallel through modules 46 - 52 to manifold 62 and then exits through moist exhaust air outlet port 64 .

Membranes suitable for use in the present invention include "hydrophilic cellulose membranes of type J" by Loeb and 5ourirajan and "Synthetic Mea+bran
es, Hyper-and-Ultrafiltra
tion Use) J (Vol. 2, American Chemical Society Symposium, Series 154, Albin F.
It is a hydrophilic cellulose membrane as described in (Ed. Turbak, 1981).

It is also possible to use cellulose membranes in dialysis form.

For various applications, the permeability of suitable membranes ranges from virtually "zero" to 20 ml/hr/mm Hg/s+" of water.

FIG. 6 schematically shows a second embodiment of the invention. This embodiment is particularly useful for industrial applications where water is contaminated with hydrocarbons, fluorinated hydrocarbons or PCBs.

In particular, the assembly of FIG. 6 includes a filter module made in accordance with the present invention that contains a number of non-porous free-standing hollow fibers of regenerated cuprammonium cellulose. There is. A storage tank 62 containing a mixture of water contaminated with hydrocarbons, such as oil, is in fluid communication with the outer surface of the membrane within housing 60 via conduit 66 . A pump 70 exerts a positive pressure on the mixture entering the housing 60 from the inlet 68 . Water diffusing through the plurality of hollow fibers is collected by gravity flow and exits the housing 60 from the outlet lower 2.74 and is directed through conduit 76.78 to a collection source (not shown). The water-separated and concentrated mixture exits the housing 60 through outlet 80 and through conduit 8
2 and recycled back to storage tank 62.

As the mixture is continuously recirculated, the mixture is transferred to tank 62.
concentrated when collected. Mixture is periodically added to tank 62 via conduit 84 . The flow of fluid mixture supplied to tank 62 through conduit 84 is selectively controlled by valve 86 .

The second embodiment of Figure 6 provides a method for separating water from a mixture of water and hydrocarbons (or a mixture of water and halogenated hydrocarbons), which method comprises introducing a mixture of water and a hydrocarbon into contact with the outside of a membrane comprised of free-standing, hollow fibers having an inner and outer surface; and allowing water from the mixture to be absorbed by the membrane. and diffusing water to the opposite side of the membrane. As above, water is removed from the second side of the membrane and ultimately directed to conduit 76.7B;
Meanwhile, the remaining mixture is removed from the first side of the membrane and ultimately returned through conduit 82 to storage tank 62 for recirculation and concentration.

Unlike conventional assemblies that use membranes such as cellulose acetate membranes, the present invention allows recycling and concentration of water contaminated with hydrocarbons, leading to membrane fouling and deterioration. You can extend your life without any problems. Conventional equipment using cellulose acetate is not capable of efficiently separating contaminated water from water and hydrocarbon mixtures, nor is it durable to continuously recycle and concentrate the mixture. Under such conditions, cellulose acetate deteriorates and eventually contaminates the equipment.

Unlike conventional dialysis devices that use cuprammonium cellulose membranes, the device of the present invention is configured to expose the membrane to fluids that are corrosive and degrading to other membranes. , can be exposed to fluids for long periods of time without deterioration.

EXAMPLE 1 In the experimental apparatus IO, a single module of the type shown in FIG. The working volume is 125 cc (0,12
54? ).

Moist methane gas was introduced into the apparatus and brought into contact with the outer walls of the fibers making up the membrane, while a sweeping stream of dry nitrogen was passed through the bores of the fibers.

In operation, the temperature of the wet methane is 80"F (
(approximately 27°C), and the dew point was 78"F (approximately 26°C). The molar flow rate of methane was 4
．． 1 x IQ-' gmoles/1llin, and the molar flow rate of water is 1. I X IQ-' gmoles
/ It was a win.

Nitrogen inlet temperature is 79 °F (about 26 °C), dew point is -7
0@F (approximately -57°C), molar flow rate is 1.9 x 10-
” gmoles/min. The temperature of the methane coming out of the device was 74°F (about 23°C), and the dew point was 4.5°F.
(approximately 15° C.) (the moisture content in this case was below the lower limit of the measurement range of the measuring instrument). The molar flow rate of water relative to the discharged methane was 6.7 gmoles/min. This indicates that 94% of the water was removed from the methane, a conservative estimate due to the limitations of the instrument mentioned above. The temperature of the exhausted nitrogen is 74 °F (
(about 23° C.), the dew point was 48° F. (about 9° C.), and the molar flow rate of water was z, axto-' gmoles/l1lin. Even after 8 hours of operation, the operating condition was not stable.

Example 2 However, in another operation, the flow rate was made very large (four times the flow rate in the above operation), and operation with a stable flow rate became possible.

In this operation, after 30 hours of operation, the dew point of the exhausted nitrogen reached 22 °F ± 1 °F (approximately -5 to -6 °C) and then remained stable, reaching a steady flow rate. It was shown that The dew point of nitrogen at the outlet is 1.5”F (
-17°C), indicating that more than 95% of the water was removed.

The above example demonstrates that the apparatus 10 of the present invention is capable of removing more than 95% of water from a stream of humid methane gas, and that 99% (
The results show that it can be estimated that water above a dew point of about -25" F (corresponding to a dew point of about -32 C) can be removed under the experimental conditions. Based on these results, the apparatus and method of the present invention can be It is believed that dew points of less than -50°F (approximately -46°C) can ultimately be achieved.

■--Water contaminated with approximately 3% heavy crude oil was passed through a module containing cuprammonium cellulose hollow fibers with a surface area of 2 mz. This contaminated water was flushed to the outside of the hollow fiber. The water immediately diffused through the membrane wall of the hollow fibers and flowed into the collection container from inside the hollow fibers under the action of gravity. The appearance of the water separated from the crude oil-contaminated water was glass-clear and water-white, whereas the crude oil-contaminated water was dark brown in color. The concentrations of toluene, xylene, and ethylbenzene were measured in the contaminated water before passing it through the hollow fiber membrane. Before separation, the concentration of toluene was 0.066Ill) II+, the concentration of xylene was 0.263 ppa+, and the concentration of ethylbenzene was 0.062 ppm. None of these were detected when analyzed using the technique with a detection limit of 0.005 ppm. A second run was conducted using the same set-up conditions, using a sample of water that was intentionally contaminated with 10 ppm of tetrachlorethylene. the result,
When analyzed using high performance liquid chromatography technology, no tetrachlorethylene was detected in the water that passed through the fiber membrane.

As is clear from the above examples, the invention can be effectively used to decontaminate water and return it to the surrounding environment in a safe condition, and the method of the invention to achieve this It has high efficiency.

Further in accordance with the present invention, a method is provided for removing water and dissolved water-soluble components from a hydrocarbon fluid.

Generally speaking, the method of the present invention involves direct contact along the length of an undisturbed, unsupported surface of a large number of hollow, non-porous copper ammonia cellulose membrane fibers.
The method includes the step of passing a stream of hydrocarbon fluid in one pass. When a hydrocarbon fluid contacts the fibers, the fibers selectively permeate only water and dissolved water-soluble components from the hydrocarbon fluid by diffusion. Water diffusing through the membrane and dissolved water-soluble components are removed from the other side of the membrane using diffusion dynamics, such that at least 95% of the water in the dissolved water-soluble components is removed from the hydrocarbon fluid. .

By continuously removing water and dissolved water-soluble components that diffuse through the membrane from the inner core (bore) of the fiber,
A membrane permeation gradient of water and dissolved water-soluble components diffusing across the membrane is maintained.

Although the present invention has been illustrated and described above, it should be understood that the terms used in this specification are the words used in the description and are not intended to be limiting.

Various modifications and variations of the present invention may be practiced in light of the above teachings. Accordingly, the invention may be practiced within the scope of the appended claims (in which reference numerals are merely for convenience and not restrictive in any way).

[Brief explanation of the drawing]

FIG. 1 is a side view, in cross-section, of an apparatus for drying a gas stream constructed in accordance with the present invention. FIG. 2 shows a partial cross-section of one of the fibers used to form a membrane according to the invention. FIG. 3 is a perspective view showing the ends of the fibers forming the membrane tied together into a bundle of tubes with the open ends of the fiber bores exposed to allow a sweeping flow of air to pass through; . FIG. 4 is an enlarged view of a portion of a membrane constructed according to the present invention. FIG. 5 shows a method using the types of membranes shown in FIGS. 1 to 4.
1 shows a multi-chamber (multi-stage) drying device according to the present invention. FIG. 6 is a schematic configuration diagram showing a second embodiment of the present invention. 10... Filter device, 18.20.22.24... Boat, 26... Membrane,
28...Hollow fiber, 36...Screen, 38...Hollow fiber wall, 40...Outer wall,
42...Inner wall, 46.48.50.52
...Module, 54...Moist gas supply port, 56...Dry gas discharge boat, 58...Manifold, 60...Dry air inlet boat, 64...Moist air inlet port Outlet port, 70...pump, 86...valve.

Claims (1)

Claims: (1) a source of hydrocarbon fluid, a dry hydrocarbon fluid collection container, a plurality of hollow fiber membranes having an inner surface and an outer surface, and a hydrocarbon from said source. and conduit means for bringing fluid into longitudinal contact with a first surface of said hollow fiber membrane and conducting said fluid to said collection vessel. ,
said membrane having a diffusion means comprised of substantially unsupported non-porous cuprammoniac cellulose with an unobstructed continuous surface to diffuse only water and dissolved water-soluble components from said hydrocarbon fluid; and removing at least 95% of the water and dissolved water-soluble components from the hydrocarbon fluid using diffusion dynamics during one pass of the hydrocarbon fluid along the length of the fiber. Apparatus for removing water and dissolved water-soluble components from a hydrocarbon fluid, characterized in that the apparatus comprises water removal means for removing water and dissolved water-soluble components from a hydrocarbon fluid. 2. The device of claim 1, wherein the average thickness between the inner and outer surfaces of each membrane is between 9.5 and 10.5 microns. 3. The apparatus of claim 2, wherein said water removal means is a stream of sweeping gas flowing lengthwise along a second of said surfaces. 4. The device of claim 3, wherein the first surface is the outer surface and the second surface is the inner surface. (5) the length of the undisturbed and unsupported surface of a plurality of hollow, nonporous cuprammoniac cellulose membrane fibers in a method for removing water and dissolved water-soluble components from a hydrocarbon fluid; passing a stream of the hydrocarbon fluid into direct contact once with the surface along the direction of the membrane fibers; A process of selectively permeating the membrane fibers by diffusing only the components, and removing water and dissolved water-soluble components that diffuse through the membrane from the other side of the membrane by making full use of diffusion dynamics, and carbonization. and removing at least 95% of the water and dissolved water-soluble components from the hydrogen fluid. 6. The method of claim 5, wherein the step of removing further comprises introducing a sweep flow in a direction opposite to the flow of the hydrocarbon fluid. (7) passing the stream of hydrocarbon fluid further comprises passing the hydrocarbon fluid over the outer surface of the membrane fiber; and the removing step further comprises passing the water and dissolved fluid from the inner surface. 7. The method according to claim 6, further comprising the step of removing water-soluble components. (8) The permeation step further comprises the step of diffusing the water and dissolved water-soluble components across an average distance of only 9.5 to 10.5 microns from the outer surface to the inner surface. 8. The method according to claim 7, characterized in that: (9) A method for removing water and dissolved water-soluble components from a hydrocarbon fluid by first contacting the moist hydrocarbon fluid with one side of a nonporous permeable membrane, comprising:
using as a permeable membrane a fibrous unsupported membrane made of a material selected from the group consisting essentially of cuprammoniac cellulose, and controlling the diffusion of water and dissolved water-soluble components across said membrane; maintaining a membrane permeation gradient and causing diffusion to remove 95% of water and dissolved water-soluble components from the hydrocarbon fluid during one pass of the hydrocarbon fluid through the membrane. A method for removing water and dissolved water-soluble components from a hydrocarbon fluid. (10) A method for drying a stream of moist hydrocarbon gas using a hollow fiber membrane, comprising: providing a membrane made of nonporous, hollow, hydrophilic cuprammonium regenerated cellulose fibers that do not permeate hydrocarbons; introducing a stream of moist hydrocarbon gas into contact with the outside of the fibers to cause water vapor in the hydrogen gas to be absorbed by the fibers and diffused into the fiber bores; introducing a sweeping gas flow into the bore to remove dry water; and removing dry gas from the membrane. How to dry the stream. 11. The step of introducing the sweep gas flow is performed by directing the sweep gas flow in a direction substantially opposite to the flow of humid hydrocarbon gas. the method of. 12. The method of claim 11, wherein the membrane-forming fibers are cuprammonium cellulose and the wet hydrocarbon gas is primarily methane. (13) The permeability of the membrane to water is 20 ml/hr
13. The method according to claim 12, wherein the temperature is less than /mmHg/m^2. (14) A method for drying a moist stream of hydrocarbon gas using a hollow fiber membrane, comprising the step of using a nonporous, self-supporting hollow fiber made of cuprammonium regenerated cellulose fiber as the membrane; introducing and contacting the stream of moist hydrocarbon gas to the outside of the fibers to absorb water into the fibers and diffuse into the fiber bores; and removing the absorbed water from the bores and the membrane. 1. A method of drying a wet stream of hydrocarbon gas using a hollow fiber membrane, the method comprising the steps of: removing a drying gas from said membrane. (15) The method according to claim 14, wherein the material forming the fiber has a water permeability of 20 ml/hr/mmHg/m^2 or less. 16. The method of claim 15, wherein the stream of humid hydrocarbon gas is primarily methane. (17) An apparatus for separating water from a mixture of water and hydrocarbons or a mixture of water and halogenated hydrocarbons, comprising a membrane means formed of non-porous free-standing hollow fibers made of cuprammonium cellulose. means for introducing a flow of the hydrocarbon and water mixture or the halogenated hydrocarbon and water mixture into one side of the fiber, the hollow fiber having an inner surface and an outer surface; first conduit means for contacting the fibers, the membrane means absorbing water from the flow of the mixture and diffusing it to the other side of the fibers;
An apparatus for separating water from a mixture of water and hydrocarbons or a mixture of water and halogenated hydrocarbons, further comprising removal means for removing water from the other side of the fibers. 18. The apparatus of claim 17, wherein said removal means comprises second conduit means for removing water from said other side of said membrane means by gravity flow. (19) the separation means includes a housing having a mixture inlet in fluid communication with the one side of the membrane means for receiving the mixture;
a water outlet in fluid communication with the conduit means, and a water outlet spaced apart from the mixture inlet for discharging the mixture from the housing and in fluid communication with the one side of the membrane means. an outlet, the device further comprising: recirculating the mixture to the mixture inlet;
19. Apparatus as claimed in claim 18, including recirculation means for continuously concentrating the mixture by removing water on each pass through the one side of the membrane means. (20) the recirculating means comprises a storage means for accommodating and storing a quantity of the mixture to be recirculated, the storage means having an inlet for receiving the additional mixture; 20. The apparatus of claim 19, further comprising valve means for selectively controlling the amount of mixture. (21) In a method for separating water from a mixture of water and a hydrocarbon or a mixture of water and a halogenated hydrocarbon, a non-porous, self-supporting hollow fiber made of cuprammonium cellulose having an inner surface and an outer surface. introducing a mixture of water and hydrocarbons or a mixture of water and halogenated hydrocarbons into contact with one side of the formed bundle of membranes, and allowing water from the mixture to be absorbed into the fibers. Diffusing water to the opposite side of the fibers, removing water from the opposite side of the fibers, and removing residual mixture from the one side of the fibers. A method for separating water from a mixture of water and a hydrocarbon or a mixture of water and a halogenated hydrocarbon. (22) Claim 2, wherein the step of removing water is a step of removing water by gravity flow.
The method described in 1. (23) recycling the mixture removed from the one side of the membrane to the one side of the membrane; and concentrating the mixture by removing water each time it passes through the membrane. 23. The method according to claim 22. (24) the recycling step includes storing the mixture removed from the opposite side of the membrane and selectively mixing the stored mixture with an additional mixture; 24. The method of claim 23, further comprising the step of: introducing into said one side.