DE2327106A1 - METHOD AND DEVICE FOR SEPARATING INDIVIDUAL COMPONENTS FROM A FLOW MIXTURE - Google Patents

Description

DR. BERS DIPU-ING, STAPF PATENT LAWYERS O *}? 7 1 Π R

β MUNICH SO. MAUERKIRCHERSTR. 48 Z O Z / I U D

Anualtsakte 23 960 2 May 8 t3? 3

Charles Uilliam Skarstrom Nontvale, New Jersey 07757, USA

3ack Kertzman Oceanport, New 3ersey 07757, USA

l / experienced and device for separating individual components from a flow mixture

The invention relates to a continuous method of separating Ausuahl- or key components from mixed fluids, uia the separation of moisture and / or carbon dioxide from air, souie an apparatus for carrying out such separations uelche pre S

is partaking. A09847 / 0701

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According to one feature of the invention, fluids are used dried by extracting water from them by means of membrane elements, which are in the form of small hollow ones Threads are made of organic polymers Compositions are made which are optionally permeable to water. In particular, the invention provides a separation device, as well as methods of operating the same. According to one feature, the invention provides cold zone at the outlet end of the column, so that the water content of the product uird uird lowered. According to another feature of the invention, a heated zone is provided at the feed end in order to achieve the maximum The ability of a cleaning gas to absorb water is increased, and the system's ability to

stretches uird, so a fluid with high dew point temperature, as well as fluid currents, uelche liquid Carry out water to dry. According to a further feature, according to the invention, a heated zone in the Middle of the column applied to part of the heat of evaporation von Uasser to remove Uasser from liquids that are miscible with Uasser, such as adding Uasser itself.

According to another feature, it is provided according to the invention) individual threads or bundles of these threads into one

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Immersing liquid containing water, through the Uasser selectively penetrates the thread or bundle of thread. In addition, the invention creates a l / experienced for Removal of water from constant boiling mixtures

One of the main advantages of the separation technique of the invention for continuously separating fluids and the The penetration column according to the invention lies in its simplicity. It is a completely continuous passive process with no circulation valves, none Time switch and no preheater required and no operating problems with replaceable books or cartridges knows »There are no solid or liquid corrosive residues that have to be removed, regenerated or closed are to be replaced or which form additional impurities in industrial waste · When using the invention for Drying air does not add any impurities to the humid or dry air, such as dust, odorants, heat, or chemical vapors and fumes, as is the case with known procedure is the case. In addition, no liquid water has to be withdrawn, as it develops as vapor.

The term "passage mass" as used here refers to that fraction of the multicomponent feed stream which is in the selectively or semi-permeable

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ge membrane penetrates, or diffuses through this or penetrates.

The term "residue" refers to the remainder of the feed stream or the product that has not penetrated. duct stream.

The terms "gas" and "gaseous" do not only refer to media that are usually referred to as gases but also to materials that are usually referred to as vapors.

The term "selection key ¹¹ or ^LT" component, such as _μ it is used herein, is meant that component or

V specify those components that are affected by the selective-

or semipermeable membrane from a stream from with

Liquid mixed feed material passes through or which is initially fed into the system

became.

The device according to the invention comprises an arrangement of a sheath and of small tubes, the latter from a polymer which is highly selectively permeable to water. The tightly fitted shell forms a channel around the tube for a countercurrent

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™ Brille j ^ ™

ongoing flow from a cleaning fluid. the The length of the device is large compared to the diameters of the sheath or tubes. Headjoints on each Arranged at the end, create tightly sealed entrances or exit for the feed stream and the clarification stream from the tubes and the envelope. That end of the Arrangement, uo the wet feed stream enters the tube and the wet sewage stream leaves the shell, in uelcher the tubes are included is the feeding end. The other end is labeled Produktande, uo the dry one Feed stream (the so-called product) leaves the tubes and the dry sewage stream enters the shell. The roles the tube and the sheath can be interchanged. That Key principle for working with this separator consists in the use of countercurrent flow to the tubes and outer sheath. The transport of Water happens across the Uände to permeate Tubes from the wet feed stream into the countercurrent dry sewage stream. If the device is made long compared to its diameter, there is a moisture- gradient exists in the longitudinal direction, which produces an effect similar to that in a distillation column. The key conditions for maximal drying of gases require that the actual volumetric sewage flow

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Flowrate is the current split volumetric flow rate exceeds at all points along the column. A very good drying of the product can be done with sufficient column length and long residence time can be obtained.

The invention is illustrated in the following description of
Embodiments, which are shown in the drawing, explained. In the drawing shows:

Fig. 1 is a broken partial view, partially in section, of the overall structure of an embodiment the invention showing a cooling jacket pushed onto the product end of the casing,

Fig. 1A shows a cross section of the device along the Line 1A in Fig. 1,

1B is a schematic representation of the device showing the use of an outer protective cover,

Fig. 2 is a broken away view of the feed end of the device with a heating jacket, which

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is pushed onto the infeed end of the HUHb,

Figure 3 is a block diagram showing hot and cold zones shows which are used in combination,

Fig. 4 is a section for an example of a device of another embodiment of the invention, in which the middle section of the envelope is heated,

Fig. 5 is a sectional side view of the sheath in Fig. 4 showing a different embodiment for heating the middle of the shell shows

Fig. 5A is a flow diagram for the i / experience and the Uor ~ direction according to the invention for the use for Drying air and / or recovering other gases from air,

Figure 5B shows another embodiment of the invention for use for drying air as shown in FIG. 5A, wherever the dry air purification flow or return flow is proportional to the dry air product consumption,

5C is a schematic drawing of an air permeation drying system; as applied in the working examples,

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Figure 6 is a flow chart in accordance with the I / experience and the apparatus of one embodiment of the invention, wherein a cold zone at the product end the device is used to improve the drying of the air by

6A is a graphical representation of the results obtained when the invention was applied to air during of operation using the air drying system without a Cold zone was provided at the product end of the device,

7 is a graphical representation of transition results obtained in a method according to the invention with the product end of the device applied in one to air drying System is cooled,

8 is a graphical representation of steady-state results; which have been achieved by varying the feed rates, with their effect on the lowering the dew point of the product is entered when the end of the product is cooled,

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Fig. 8A is a graph showing that a lower dew point for the product by cooling bzu. Freezing can be obtained,

Fig. 9 is a flow chart in accordance with a second embodiment according to the invention, wherein self-clearing and heating of the food end of the casing is used,

Fig. 10 is a flow chart in accordance with the second embodiment of the invention, wherein the The food end of the shell is heated and an external one Sewage stream is applied,

Fig. 11 is a graph for drying uon oversaturated feed streams with ambient air, which shows that ambient air for oversaturated Feed streams can be used as sewage streams, resulting in a less dry product,

Figure 12 is a graph showing progression the cold zone towards the end of the dry product, which warns of a breakthrough,

Fig. 13 is a graph showing the effects the use of a heater at the feed end

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shows how to manipulate feed streams with a high dew point,

₀ Figure 14 shows a graph uelche multiple effects by dia Permeationsdestillierung van water so described apparatus is used uobei that shown in Figures 4 and 5 and _o in connection,

Fig. 15 is a graphic representation of the effect of the application of desiccant feed streams and the application of a sewage cover around the outer Uands of a device according to the invention,

16 is a graph showing operational data for various passage materials in drying columns in accordance with the invention,

Fig. 17 is a graph for an extreme

Drying, which is achieved by using low flow rates for the feed stream in a process and a device according to the invention is obtained,

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Fig. 18 describes a flow method for
the use of a single hollow tube
or a bundle of tubes without any
a tightly fitted cover is present,

FIG _o 19 is a graph depicting the effect of applying a sewage gas to remove
Water from the flow material,

Fig. 20 is a graph showing the effect of maintaining a minimum intake.
pressure for the sewage flow shows

21 is a graph showing the effect the sewage inlet flow shows

22 is a graph showing the effect of the sewage gas indicates the increase in water transport, and

Fig. 23 is a diagram showing that the Sewage flow-driven water transport is proportional to the steam pressure of the water.

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According to the invention is a continuous l / experience for the separation of selection or key components won Multi-component flow mixtures created, whereby the following process steps are carried out:

a) A teaching component flow mixture or a feed flow, which or which has one or more key components is determined with a predetermined, initially relatively large pressure along and in contact with the surface of one or more semipermeable membrane-like hollow limbs guided along or made to flow, which have a greater length than diameter and which for the Selection or key components of the feed stream are permeable.

b) A second fluid stream is under lesser Pressure and with a different composition than the feed flow in countercurrent or opposite to the flow of the feed stream from this through the walls of the semi-permeable, membrane-like hollow member s with a Out of flow rate which is at least substantially equal to the flow rate of the feed stream, so that the selected or key components of the feed stream (passage mass) are removed by permeation,

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whereby a pressure gradient and a concentration gradient are transverse to the walls and along the walls of the hollow member s is generated and the passage of the selectively / Passable components of the feed stream (passage mass) favored by the walls of the hollow member s and the entry into the second fluid stream uird.

c) The fluid product (residue, which is essential contains fewer permeable selection components than are present in the feed stream deducted

This improves the drying capacity of the device the hollow member will be along selected parts thereof either heated or chilled.

The mentioned second fluid flow can have a portion of the product stream with or without additional clarifying agents and can therefore be viewed as a reflux flow. However, if desired, can the second fluid stream should be independent of the product stream, but should not contain any components, which pass through the walls of the hollow member or enter them and thus contaminate the feed stream.

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An unexpected phenomenon was observed when the The product end of the casing is surrounded by a cold zone. By using a cold zone around the product end of the casing, lower dew points of the product could be obtained will.

This technique is applicable to all fluids above their melting points, such as various organic and inorganic solvents, hydrocarbons, fluorocarbons, chlorocarbons, chloroprenes, freons and other liquids. Gases such as air, nitrogen, HCl, SO ₂ , HF, HBr, SF _g , Cl ₂ , Br, NH ₃ , inert gases, and the like can also be dried using this technique.

"Drying" is generally understood to mean the separation of selected or key components ·

This particular embodiment of the device mentioned above is shown in Figures 1 and 1A, where the reference numeral 10 is a plurality of hollow permeation tubes denotes, which are provided in the form of a tube bundle with a feed end A and a product end B and in a closely fitted outer shell 12 are included. It should be noted, however, that the tube bundle 10 without

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Outer shell 12 can be used. 3 of the end of the tube bundle is held within the shell by support means, uie the head pieces 14 and 16. The device is with Line connections 18, 20, 22 and 24 equipped for the passage of the feed fluid, the product stream and the reflux or clarification flow through the shell and tubes are provided. Uie shown labeled reference numeral 18 the inlet for a feed fluid mixture which is connected to the hollow members or channels of the pipes 10 near the feed end A communicates. The product outlet 20 is connected to the pipes the product end B. The inlet 22 for the reflux or clarification stream is in communication with the area 60 between and around the tubes 10 and the outer shell 12 and is in placed in close proximity to the product end B of the device. The outlet 24 for the reflux or sewage flow is in communication with the area 60 to be admixed with the pipes 10 and the outer shell 12 and is located in close proximity to the feed end A of the device. The ends of the device come with end seals 26 and 28, souie ferrules 30 and 32 are sealed using conventional techniques.

A cooled hollow jacket 34 is arranged around the casing 12 at the product end. The dumbbell is set to the point you want

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Temperature by means of suitable devices not shown chilled. The cooling jacket extends up to a maximum of half the length of the shell. The l / device shown in FIG also comprises at the feed end Λ and at the product end B a collection space or area 36 and 38, respectively Collection space 36 serves to distribute the feed fluid mix from the feed inlet 18 into each of the permeation tubes 10. The collecting space 38 is used for collecting of the product emerging from the permeation tubes 10.

The product outlet 20 is in communication with the product reflux line 40 and the reflux inlet 22. In the reflux line 22, a valve 42 is provided so that a The amount of product from the product outlet 20 can be metered in and withdrawn to achieve a low clarifying pressure, d. H. a pressure which is less than the pressure in the tubes 10. The reflux inlet 22 is also available in connection with the sewage flow inlet line 44 which has a control valve 45 which is a combination from a regulator to reduce the pressure and a flow control valve to control the flow of the sewage stream coming from the outside into the reflux inlet 22 may be.

To carry out the method according to the invention with a The device according to FIG. 1 can be a part of the

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Duktauslaß 20 outflowing product stream 'withdrawn and passed through the control valve 42 to reduce the pressure to a predetermined value and then through the reflux inlet 22 is fed into the space 60 between the tubes and the outer shell 12. The one through the Discharge line 40 withdrawn through the valve 43 product portion is fed to a product storage container or. consumed. The balanced return flow contains all product components including water vapor at a lower total pressure, so that each component of the return flow, in the present case water, has a lower partial pressure than in the high pressure feed phase. Thus is a Pressure gradient and a concentration gradient for each component across and along the walls of the permeation tubes 10 present, which causes the presence of driving forces for the permeation of water. The per- meation tubes 10 are made of a material which has a relatively high permeability for water, the water passing through the walls of the permeation tubes 10 penetrates at a much greater speed than other components present in the feed stream. Additional Sewage gas is fed in the required amount to the inlet 22 from the line 44 through the valve 45.

In this way, the high pressure phase at the end of the product gradually becomes poorer in water and the return flow becomes with it

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Water enriched. Uenn the return flow in the envelope flows in countercurrent to the feed end A of the tube bundle, its enrichment with water is greater «. Slowly emerges a composition gradient running in the longitudinal direction along the entire tube bundle. Depending on the type the material for the semi-permeable pipes and the water content that needs to be separated from the feed stream should, uird in a period of several hours up to a constant state for several days. The result is that the product has a low concentration of water and the return flow have a high concentration of water.

By the proposal according to the invention, the shell 12 on the Cooling product end B of the tubes changes this constant state to a better condition and enables it is to obtain a drier product than in a case where the cooling jacket 34 is not attached to the device is provided.

Another embodiment of the product end B of the device according to the invention is shown in FIG. 1B, including a Outer jacket or an outer cover is used, which surrounds the outer shell 12.

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According to the device in FIG. 1B, a jacket or a Outer cover 348 arranged in the form of a shell or an outer tube around the outer shell 12, whereby a Gap or space 350 is formed between the outer shell 12 and the jacket or outer cover tube 348.

A line 352 is connected to the space 350 between the outer shell 12 and the outer cover pipe 348, as well as to the rear flow inlet 352a, 322a in connection, which flow- control means or valves 353 as shown. In addition, the line 352 is in connection with the clarification line 352b, 345a which, as shown, has control or valve means 353a and 345b. An external sewage pipe 344a, 344b, which has pressure regulators 349 is in communication with line 352b, 345a as shown. A valve 353 controls the flow of the return flow into the line 352a, 352 and the space 350, which is the outer shell 12 surrounds. Valves 353, 353a and 345b can be adjusted to allow flow of the residue from the Reverse flow extraction 22 is permitted through line 345a and a mixing of the return flow coming from the outside is achieved with the residue, as well as a flow of the mixture in the line 352 and in the space between the Outer shell 12 and the outer cover tube 348 is achieved. Uie can be seen, the valves 353, 345b, 353a and 349 can be set so that only the inflow

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on the clarifying agent flow coming outside into the room 350

is allowed. This embodiment is particular It is advantageous when extremely low dew points are desired, with the outer shell 12 being slightly permeable to Can be water vapor.

If desired, the embodiment in FIG. 1B can thereby be modified that the outer clarification line 344a, 344b and the pressure control device 349, as well as the lines 352b, 345a and valves 353a and 345b can be omitted.

The outflowing backflow in the previously mentioned method and device, which has a high concentration of highly permeable components can be deposited or it can, if desired, be compacted and / or condensed and back into the high pressure phase of the fluid feed mixture be introduced after the condensate has been removed. Alternatively, if the in the reverse flow phase or, in this case, in the clarification phase coming from the outside, existing passage components are further concentrated are to be used a stripper stage, the feed of the raw material flow between the stripper and the trigger sections. The recompressed return flow medium, which runs through both sections

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has crossed, is directed into the bottom of the strippar and Highly concentrated penetration components present in it can be drawn off from the bottom of the stripper.

In large plants, the expansion of the residue at point 42 can be achieved in an expansion machine cooling and mechanical performance. The cooling results in a pre-drying of the wet feed stream achieved. The generated mechanical power can be used for the compressors for the feed stream or the incoming Clarifying agent stream can be used.

The method and the device according to the invention can be integrated into a continuous operating system, which is intended for the production of a specified composition from a certain stock of foodstuffs is. For example, a feed mixture can be introduced into a permeation column device according to the invention uerden and part of the residue obtained in this way can be returned and in countercurrent behind the permeable Pipes, which carry the supply current, are routed. The key components from the feed stream penetrate into the pipes in and are discharged by the return flow or sewage flow. The return flow including the passage mass can then be introduced into a stripping stage,

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which creates a penetration mass that is even richer is the permeable components, and the residue is similar to another permeation stage or a Stripper stage introduced, there is a remaining mass manufactures that is poorer in more penetrable components. Such a system is in some ways in its flow pattern very similar to a multiple fractionation column. You can also use different membranes with different Use permeability and different separability in selected sections of the system, to minimize the number of stages or to maximize the purity of the product.

In the drying of fluids where the method and apparatus according to the invention are applied the volumetric flow ratio between optimal sewage flow per feed flow is greater than 1 and is preferably in the range of about 1 and a total return flow that is used for self-cleaning. The actual volumetric flow rate for the return flow can be determined according to the following formula!

P / F χ (R ₊ D) R (PHi ^{/ p} Lo)> (1) R = or P / F = = 1

PHi / PLo χ R ₊ D

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uorin R denotes the flow rate for the return flow, which in volumetric standard units per unit of time is measured, e.g. B. according to the American abbreviation scfm, uorin D is the proportion of the flow rate in the total product denotes which was withdrawn from the system for external use and in the same Standard units of how R is measured, uorin p ^ the full Pressure in the high pressure phase at the product end of the system, regardless of the manner in which the withdrawn to the outside Product removed. Be it at full pressure or under reduction by a valve or a pressure regulator, designated and in absolute pressure units, uie the American unit of pressure is measured as psia, where pi is the pressure in the low pressure phase at the end of the System designates into which the return flow or the supplied sewage flow flows and in the same absolute flow Pressure units like t ^, as in American printing— unit psia, and where P / F is the ratio of the actual volumetric flow of the return flow or clarification flow to the current volumetric flow of the feed flow and is equal to or greater than is.

If the feed fluid mixture is un- is a miscible liquid, equation (i) assumes a sub-

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different farm. An additional sewage flow is required if the water is compressed when it is in the liquid Strümmittelstram is relieved. In one In the event that part of the liquid product is evaporated, so that it acts as a clarifier at a pressure p. serves, the equation takes the following form:

(2) eR = (P / F) χ (R + D) x H _f ,

where e is the volume expansion ratio of the clarifying agent, uelches is evaporated and brought to the temperature of the permeation column, where H _f ^is Henry's solution constant for the volatile permeable component in the form of a ratio of the space charge density of the component in the solution state to that in a gas space in Equilibrium with the feed stream at column temperature. In the case of a liquid feed stream, where the return flow medium is a suitable gas or vapor, the clarification flow should exceed the feed flow in 3/4. For a suitable liquid for the clarifier _{flow, H f} modifies its minimum required flow rate.

The volumetric feed flow rate is determined at a pressure at which the feed stream passes through the pipes. This rate is made up of the tear results of a

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atmospheric water cooler for the product and the flowing clarifier is calculated and gives the current volume of the feed stream per ['' iinutB, Jenn the result was determined by the internal volume of the tubes, a feed flow rate in puree pressures of the actual volume of the Feed flow found per minute per volume of the tubes, abbreviated V / v / min. For best results it is preferred a feed rate in the range of 0.01 V / v / min to 100.ODO V / V / min used.

In general, when carrying out the process of the invention, the pressures that can be used in the high pressure phase or the mixed feed fluid phase are determined by the mechanical strength and dimensions of the permeable hollow members or tubes and the outer shell. Pressures from below ambient to about 1,000 atmospheres can be considered feasible when using small diameter pipes of about 0.05 to about 12.7 mm or more. The pressures in the high pressure phase and in the low pressure backflow or clearing phase can be below atmospheric pressure as long as there is a pressure difference between the two phases. The lower pressure phase or return fluid should have a pressure ranging from about 90 % to less than about 1 %, and preferably about 50 / Ό

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or less of the pressure in the high pressure phase, if a self-clearing u is used. If a sewage stream coming from the outside is used which is essentially free of water, the sewage stream coming from the outside can have a suitable pressure which is higher, lower or equal to the pressure in the high pressure phase. The pressure of saturated water vapor at ambient temperature can be used as the lower limit for the clarifier pressure. In general, depending on the equipment used, when drying air, the high pressure phase or the feed phase should preferably be under a pressure which is in the range of about 1,000 atm to about 2 atm absolute, and the low pressure phase should preferably be under a pressure which is about 50 y _{Is 0} or less than that of the high pressure phase, and is preferably atmospheric pressure. It should be noted, however, that an atmospheric pressure clarifier stream or reflux stream can be used at a feed pressure which is near atmospheric pressure.

For the operating temperatures and the temperatures of the feed fluid mixture and the reflux or clarifying fluid the upper and lower temperatures are dependent on the thermal stability and maintenance the permeability of the permeable material used ^,

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Accordingly, temperature can be employed in the range of etua -50 ⁰ C to +400 C etua. However, temperatures outside these temperature range limits can also be used with a special semipermeable membrane-like material.

Learn about the above and the above device noted that the feed fluid flow in the space formed between the outer shell and the tubes, d. H. through the shell, introduced and daO the reflux stream or clarifying agent stream can be passed through the tube bundle in countercurrent. However, sometimes it is advantageous that the phase with the higher pressure, i. H. the feed fluid mixture, inside the small ones Hollow links or tubes are introduced rather than through the wide envelope to avoid the need to form envelopes that can withstand high pressures.

The P / F ratio of clarifier to feed stream is in the range from greater than 1 to total reflux - current. An increased P / F ratio is better able to reduce the dew point of the product from daily changes the ambient temperature and humidity level at the feeding end of the column. At one company in a steady state with a total reflux flow, the maximum drying capacity of the pressure system is

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and flow conditions.

In another embodiment of the invention, FIG. 1 shows a heating jacket 11 which is arranged around the casing 12 'at the feed end A ¹ . The head piece 14 ', the tube bundle 10',. the conduit connector 18 ', 24', the plenum 36 'and the end seal 26', as well as their required counterparts, are all connected to the product end B in the same manner as shown in FIG. 1 and described in connection therewith.

This heating mantle is able to expand the column capacity so that feed streams with higher dew point temperatures can be processed, including feed streams that contain entrained Uasssr.

The temperature of the feed end A ^{1 is} maintained at a temperature greater than that for the product end of the column and that is in the range of from -17.5 to 93.5 C (1 to 200 ° F), and preferably from -6.1 to +37.8 ⁰ C (20 to 100 F)

lies.

So that feed streams with high dew point temperatures can be processed, it has been found to be desirable is to heat the column at the food end.

ORIGINAL INSPECTED

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As shown in Fig. 3, a wet feed stream is in front of it Entry into the heated zone 46 of a suitable column heated, the feed stream then passes through a plurality of zones 47 to 52, which progressively cooler until it reaches the coolest zone 52 at the product end of the column. It is also possible to use the clarifier or Pre-cooling the return flow (during self-clarification). before it enters the column at the product end. Also will advised that additional preheated clarifier introduced into the column at any convenient location can be"

The third embodiment according to the invention relates to a case in which a clarifying agent stream of dry gas countercurrent to initiate evaporation and cooling a liquid feed stream is used which contains miscible water, the feed medium stream in the middle of the column is heated and the condensation heat of the Uasserdestillatas to preheat the liquid Feed medium flow is used at the bottom end of the column.

This embodiment is shown in Fig. 4, which is a multiple operating continuous water desfcillation column shows or envelope 54 comprising a bundle of tubes 56,

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which consist of their signed material, which selective / permeable to water.

4, the envelope 54 is mounted at an angle to the vertical to ensure the removal of air pockets from the garbage by causing the liquid feed stream to flow upward. A plurality of hollow permeation tubes 56 are disposed within the envelope. A tightly wound heating coil 58 is attached around the envelope in the middle of the column. The heating coil is positioned to create a heating zone 59 equidistant from each end of the envelope 54. At its center point, the temperature of the heating zone is measured by a temperature sensor 62 (e.g. a thermocouple). A signal is passed via line 64 to a temperature control device 66 which maintains the temperature of zone 59 at a predetermined value T. A pumping device 68 maintains the continuous circulation of the liquid feed stream through the sheath 54. Temperature sensors (thermocouples) 70, 72, 74 and 76 are rings of the casing for measuring the temperatures at the feed fluid inlet and outlet reasonable ^r arranged to be read on a Uielpunkt temperature display device 78 at right places.

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A dry clarifier stream (air) is over the pipe 80 introduced into the interior of the tubes 56 and via the Line 82 led out into a separator 04, valves 86, which are arranged in line 80, hold one suitable pressure in the clarifying agent flow in the pipes and also the counter-rotating clarifying agent flow through the tubes 56 upright. A wet meter (not shown) measures the clarifier flow. Multiple requests are made, to determine the leak tightness of the envelope 54 and the tubes 56. Insulation is provided around sheath 54 appropriate to avoid heat losses. Temperature sensor 88 and 90 measure the inlet and outlet temperatures of the clarifier stream.

The liquid feed stream enters the envelope 54 Ambient temperature and the dry clarifier stream enters tubes 56 at the top of envelope 54. Both of these streams are heated as they pass through the heated central zone 59. The liquid one Feed stream leaving the hot zone is converted into the dry clarifying agent stream by evaporation of its water chilled. The liquid feed stream entering the hot zone from the feed end is through the ■ Condensation of water from the clarifying agent flow uorgeujarrnt, which emerges from the hot zone. In the ideal case

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enter the feed means and the sewage gas in and out of the permeation Destillierhülle 54 at approximately the same temperature, with preference ambient temperature BZU _o from _a the heater 58 provides Uärme merely for Ausgigich of insulation losses and any low thermi rule imbalances of the system. As a result, the shell 54 is divided into an evaporation zone 92 and a condensation zone 94.

The distilled feed condensate exits the pipe with the wet clarifier stream via line 82. The liquid spaiso exits via line 96 at the end of envelope 54 where the dry clarifier stream enters. This exiting feeder medium flow has a reduced water content, since it was partly dried to an extent which corresponds to the water vapor _{and was discharged by the sewage gas or similar}

Adiabatic evaporation of the water from liquid water creates a cooling of the mixture and also reduces the proportion of water remaining in the mixture. In the evaporation section 92 of the envelope 94, water enters the hot zone at a temperature T (hot) and at a rate Fl? 9A ¹ ^ n a, When passing through the evaporation section, an evaporation of C g / min reduces the water content of the feed to R ₁ g / min and

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cools it from T (heio) to T (cold). The above appearance can be described by the following formulas:

H
/ ₃ \ _lr) / \ = In (I + C / IMjl) - In (1-CA ^- I ₂ ) =

M ₁ S [T (hot) - T (cold) l

Therein In is the natural logarithm, 3 the middle one specific heat of the feed water mixture or L is the mean latent l / heat of vaporization of water from the liquid foodstuffs.

This formula does not indicate how much water can be evaporated by this type of device. she describes but only the adiabatic cooling effect in terms the ratio of water evaporation to water circulation flows. She contributes to the experimental Setting the operating variables for thermal equilibrium at.

Fig. 5 shows another embodiment for heating the center of the envelope described in connection with FIG.

In this embodiment, the sheath used has two separate sections, an evaporation

409847/0701

- 34 - ■

section 98 and a condensation section 1QG. The tube bundle 102 in the evaporation section can, if so desired, be made of a different material than the tube 104, which is arranged in the condensation section. One The hat heater 106 heats and controls the temperature of the flowing feed-water-mixture. In the event of an management form uar dia heating device 106 a hot water bath, which has a copper snake 108 and an immersion heater 110, and temperature measuring means 112 associated with temperature control means 114 were connected. The hot water line 116 enters the shell section 98 and exits from the condensation section via line 118. Temperature measuring means 120 and 122 measure the inlet and outlet temperatures of the circulating water.

It is pointed out that other heating means can also be used here and that this is also experienced discontinuously or carried out batchwise with returned liquid or continuously with a series of columns can be adjusted to a desired degree of dryness for the water mixed liquid in one step to get through the system. The emerging sewage gas can be returned when the condensate has been removed, and with a series of columns, the same sewage gas can be used in all of these columns in succession, whereby the water condensate removed between the individual stages

409847/0701 -35-

will. When the system operated above atmospheric pressure ulrd, the temperature of the hot zone can be above the boiling point at atmospheric pressure for greater water transport through the walls of the permeable material.

In the embodiments according to the invention in which a If a single column is used, it is advantageous to seal the flow for the liquid feed stream in the envelope to be placed near the heater, whereas in the case of a composite Column and an external heater, the shell and the pipes can be interchanged, as well as in the other embodiments according to the invention.

The following table gives the various drying applications for the invention to:

- 36 409847 / 070T

SPEISi-; ¹ DDYY.

RECOMMENDATION LiERASS DLn ¹ MÜH- LYING OFFENBAKUNG___

ERGEONIS

F _n I ₁ U _- S si fl.kei.tenji

Uasser - mixable

Cannot be mixed with aJassar

in i t oeri ss an a

in immiscible liquids

in gases

saturated at or below half-good-value

saturated above ambient condition

sleeps azo

Hittel heater

I feel the product

(essential) for a lot of entrained water

Heating dos üpeisaendes and Cooling the product end (optional)

! ■ laizen det; Food and Cooling the end of the product

Cooling the l ^J roduktendes

(especially for such high dew points of the spa medication) Heat the dpaiseandes and Cooling the end of the product (optional)

.f>!,. 'iio o.in «

Distilled Uassar from Klärrnittelaus ™ ingress current

plus product drier than

jfood

better dried product

better dried product

better dried product

better dried product

better dried product

5A shows a flow diagram of a substantially complete System constructed in accordance with the invention and for separating impurity mixtures and especially for removing moisture and / or other key components of Air serves. Referring to Figure 5A, wet air is fed into a compressor introduced and compressed to a preselected relatively high pressure, such as, for example

2 a pressure in the range from about 3.5 to 10.5 kg / cm. The compressed wet air can be stored in conventional storage until used. The compressed wet air can be further treated, if necessary, to remove oil, e.g. B ₁ in that the air is passed through activated carbon or other conventional means. Additionally, water droplets or excess moisture can be removed by passing the air through a cooler, dehumidifier, filter and / or water trap, or other suitable means. After such a treatment, the compressed wet air should not contain any water droplets, but it can still be saturated with water. The compressed wet air thus treated can now be introduced into the permeation separation column and treated as described above.

- 38 -

4 09847/0701

At a time when little dry air is consumed, so as at night, an excess of clarifying agent would become indispensable Mean load on the compressor. If desired, the permeation drying system described above can be used be adapted so that the clarifier or reflux flow is proportional to the product consumption in dry air. In such a case, an embodiment as shown in Fig. 5B can be applied. '' During the time in which the compressor is operated, the pressure To replenish in the dry air storage tank, the permeation dryer dries and clears. Urgent the compressor is switched off, an adjustment valve prevents the product storage container from flowing back Product from the tank and stop the flow of cleaning— medium flow to the expansion part of the column. The extent of the clarifying agent flow is determined by a The output of the compressor can be adjusted, such as a metering diaphragm. This arrangement creates a clarifying agent stream, which is proportional to the consumption of dry air.

The device according to the invention can have any suitable shape or design depending on the required application, You can have the shape of an elongated tube, which in a tightly fitted elongated outer shell

- 39 -

409847/0701

is included, so that he builds a Fiantel— and riohruärmetaters resembles. The tubes and the shell can coiled or in a stacked configuration, as used in spaces with limited space got to. In addition, the entire apparatus or system or any part thereof can be a protective housing or a Have protective cover to create mechanical protection «

It should be noted, daf3 the l / orrichtung gemäi3 invention with a conventional instrumentation to be used may be vorbessern to performance and / or efficiency to vergröi3ern _e 3o example, the Loitung for the feed stream mixture heating means comprises to either the feed stream to the Bringing the ambient temperature for the permeation separating device or preventing the liquid feed stream from freezing. In addition, the line for the clarifying agent liquid stream can also have heating means for the same purpose. Alternatively, it may be desirable to cool both the feed stream and the clarifier stream in order to take advantage of increased selectivity or permeability of the fiembran at low temperatures.

The semipermeable membrane-like materials, uelche er— Can be used according to the invention in the form of the above

409847/0701

_ 40 -

mentioned hollow members or tubes allow the passage one or more key or selection components the liquid feed stream mixture and provide a high for the other components of the feed stream mixture Resistance or they are impenetrable for this, The semipermeable, membrane-shaped material should be chemically be stable when dealing with the various components of the feedstream mixture and also the reflux and / or clarifying fluids is in contact. In addition, it should have sufficient mechanical strength and flexibility, in order to be able to withstand relatively high pressures and in order to be able to withstand during shipping and during actual use a separation process without breakage to be handled can.

Normally it would be necessary to use the semipermeable Cut membrane for special separation applications « The selection of the semipermeable membrane depends on the key or selection components that are made up of to be removed from a feed stream mixture, as well as from the composition of the rest of the feed stream and the required penetration rate of the key components. The rate of penetration of the key component through the permeable membrane is determined by the chemical composition the membrane, the temperature of the feed stream mixture, the

- 41 -

A 0 9 8 4 7/0 7 0 1

effective surface area is the membrane and l ^v iembrandicke controlled. The choice of membrane is different depending on whether the feed fluid mixture is gaseous, liquid or a mixture of liquid and gas.

Semipermeable membranes, which are particularly advantageous for the drying of fluids according to the invention contain hydrophilic polymers. For example, the following are advantageous: Perfluorosulfonic acid polymers and silicones such as: dimethyl silicone, methyl vinyl silicone or Nethyl uinyl silicone j. cellulosic substances such as cellulose acetate and cellulose propionate or cellulose butyratej nylon such as Nylon IU, nylon UI and nylon Ulli, as well as hydroxy-diethyl-dietary acrylate and isocyanates such as copolymers of toluene diisocyanate, and glycols or polyesters such as Polyurethanes, polymers like polystyrene, polypropylene, polyethylene which is modified to be hydrophilic Properties due to sulfation, sulfur chlorination or by using comonomers such as carboxylic acid and get salts from it.

Hollow links or tubes made of semipermeable ^ material are intended be much longer than their diameter. This is so in order to have the appropriate concentration gradient along the length of the pipe can be maintained.

- 42 -

40Ö847 / 0701

The cross-section of the tubes can be of any convenient configuration have, like circular, rectangular, triangular, elliptical or other polygonal or rounded designs » In addition, the tubes can be corrugated, corrugated or corrugated to the effective surface of the semi-permeable Uands to increase. If desired, the semipermeable (materials coated or supported with a permeable backing, such as made of fiberglass or metal grilles or standard filter materials. aside from that the hollow member can be a hub construction which is designed so that it can feed the flow of feed and / or carries the reflux or sewage stream.

The outer shell should have sufficient mechanical strength to withstand the pressures between the tubes and of the envelope, and it should be substantially inert to the components of the reflux fluid, des Clarifying fluid or for the components of the feed stream mixture if the feed stream flows through the shell instead of through the tube bundle. So can the outer shell depending on the intended separation of materials uie polyethylene, polypropylene, polyvinyl chloride, various Fluorocarbon polymers, butyl rubber, neoprene, metallic foils such as aluminum or copper foils, a metal tube or made of glass. The outer tube or

- 43 -

409847/0701

the outer shell is preferably designed in such a way that sis is impervious to the surrounding atmosphere and to the fluids flowing in the outer shell.

The head pieces 14 and 16 are preferably made of plastic. ■ made, as well as from epoxy-polyamide, silicone, polyester or from fluorocarbons, but they can also be made of some solid structural material, which the tube bundle, can carry. · ...

The end seals 26 and 28 are preferably made of a non-expanding plastic material such as _: polyethylene, polypropylene, fluorocarbons, butyl rubber, Buna-N, or neoprene; however, they can also be of any suitable conventional material, such as for. is apparent to the person skilled in the art _o -,

The Speisemitteleihlaß, the _{Rückstandsausiaö:} the Rückflußstrom- or Klärmittelstrom inlet or outlet may be of any conventional tube material, such as stainless steel, aluminum, copper, nylon or polycarbonates.

For the above-described method and device it should be noted that the feed flow into the space formed between the outer shell and the tubes, i. H. by the outer shell, and that then the reflux

4098Λ7 / 0701 .... - 44 -

- .4 4

or Klnrstrom in the Gsoonstrorn through which μοΙιγρΠπΗ ^ ι .nnn leads. In the practical case, however, it is drawn that the phase with the higher pressure "d _o hu the 3p" i3destJmunnsmittelgamiseh, through the small hollow belts or pipes rather than through the large envelope be performed · ;, the Notusndigkoit ■ to vermniden _s design the AuGenhülie so da.3 withstand hohsn Press.

The l / learn and the device according to the invention can for the separation of gaseous materials, as for the separation of water from air, the separation of rare gases from air, the separation of carbon dioxide from air, the separation of oxygen or nitrogen from air, the separation of carbon disulphides from air, the separation of moisture and carbon dioxide from Hethane (natural gas), the separation of carbon tetrachloride from air, the separation of acetylene from air and generally the separation of helium, Hydrogen, nitrogen carbon monoxide, nitrogen oxides and argon from mixtures with larger-molecular gases uerden. They can also be used for the separation of liquid materials, as well as for the Dehydration of propane (LPG), butadiene, isobutylene, alcohols, aromatic solvents and fluorocarbons, as well as for the separation of gaseous and liquid materials. uie. for fission products of sulfahexafluoride, if

ORIGINAL INSPECTED

409847/07

- 45 this is used as a dielectric.

If the feed fluid mixture is gaseous, u will the process by which uelches the key - ^ - or selection components to pass through the permeable membrane »theoretically regarded as diffusion. But there is Feed stream mixture of v / mixed liquids, the theory applies that the liquid key component, which is to be separated from the remainder of the liquid feed stream is solubilized in the membrane into which Membrane in the direction of the low 'pressure or uo the reflux phase is, diffuses and from the membrane on that i'iembranssite, which the fluid mixture is discharged, desorbed and carried by the reflux fluid led away.

The device according to the invention may take any convenient form or arrangement as required Use case. It can have the shape of a long pipe, uelches in a tightly fitted long one Outer shell is included, similar to the arrangement of a jacket and tubular exchanger. The pipes and the envelope can be closed or opened multiple times, uo be used in rooms with limited space. In addition, the entire apparatus or the entire system can be used

- 46 -

409847/0 70 1

23271

or each part of it comprises a protective housing or a protective cover against mechanical damage.

In another embodiment, which in particular for drying of a material, such as an acid, which is highly corrosive, becomes a single hollow tube or used a bundle of tubes without a tightly fitted envelope.

Referring to Fig. 18, a tube bundle 503 was placed in a container 501 which received a fluid which is either gas or liquid with water in it

The hollow links or tubes should be much longer, than its cross-section in order to maintain the appropriate concentration gradient along the length of the pipe can. The cross-section of the tubes can be of any convenient shape, it can be circular, rectangular or square, triangular, elliptical or any other 5 / corner shape. In addition, the pipes can be grooved, be corrugated or ribbed in order to increase the effective surface of the semipermeable walls.

The tubes 503 are immersed in a wet fluid 504, which is received in a container 501,

409 84 7/0701 - 47 -

uelcher is mounted on a heater 505, the temperature of which by any suitable temperature control 507 is held.

A clarifying fluid is made up of one not shown Source by a flow control device 509 via the Line 511 out, passes a pressure indicator 513, uird passed through the pipes 503 and comes out of it via the Line 515 off and cooled in a cold zone 517, from uelcher via line 516 the water is condensed into a container 519. The pressure of the sewage flow- means is in the range of O, ÜÜ7 at to 3.5 at and preferably from 0.14 to 0.7 at.

The application of a gaseous clarifying agent flow is required} to prevent water condensation inside the pipes. This means maintaining a sufficient clarifying agent flow, so that the clarifying agent emerging from the tube bundle for the temperature of the butter liquid is unsaturated. In this case, no liquid water will form inside the pipes. It is one Driving force for permeation is present along the entire length of the tube bundle. This condition mined also the minor transport of certain [Materials through the pipe walls when liquid water is present

- ■ 48 -: ■

409847/0701

Λ D

is present on both surfaces.

The clarifying agent can be heated before it enters the pipes 3Ü3. The lubricant containing the yeast can also be heated. The temperatures of the flow medium are preferably in the range from its freezing point to its critical temperature, preferably in the range from 15.5 to 149 ⁰ C (60 to 300 ° F).

The stocking material can be Jasser itself or it can consist of different gases or liquids that contain water, such as bleaching acid, bromine, fluorine, organic and inorganic solvents such as benzene, isopropanol, sulfuric acid, ethylene glycol and glycerine »

Although this' l / experienced as a step procedure or post procedure When it has been written, it is pointed out that it can also be used as a continuous or semi-continuous process what can be done 'the professional Chemical engineer's experience can be left to it as a continuous drying process or can be designed as a water distillation process.

Contains a preferred material for making the tubes a solid perfluorocarbon polymer containing either sulfuric acid or sulfonate groups or sulfuric acid

409847/0701 - 49 -

and has sulfonate groups. In this perfluorocarbon polymer, the countergroups are either attached directly to the main polymer chain or to the perfluorocarbon side chains attached to the main polymer chain. Either or both of the main polymer chains and each side chain can have ether linkages. The perfluorocarbon polymer from which the tube bundle 10 is made includes perfluorocarbon copolymers which have the opposing groups listed, as well as perfluorocarbon polymers which have mixed chlorine and fluorine substituents with the number of chlorine atoms no more than about 20 '} der total chlorine and fluorine atoms with the listed opposing groups. The perfluorocarbon polymers used for the tube bundle can be prepared as described in U.S. Patents 3,041,317, 3,282,875 and 3,624,053. The preferred perfluorocarbon polymers are prepared by copolymerizing perfluorovinyl ether with the formula FSO ₂ CF ₂ OCF (CF ₃ ) CF ₂ ⁰ Cf = Cf ₂ ^and tetrafluoroethylene, the -SOgF group then being linked to either a sulfuric acid group or a sulfonate group or both . The equivalent weight of the preferred copolymer is in the range from 850 to 1450, the equivalent weight being defined as the average molecular weight per sulfonyl group. The preferred thickness of the wall of the hollow member is in the range of 0.0254 to 0.381 mm.

- 50 - ■

409847/0701

The following examples illustrate the experience and the device according to the invention. The apparatus used for carrying out the method in each of the examples is shown in FIG. 5C and is composed of a compressor 370 which is connected to a storage container for compressed air via a line 374, the storage container 372 being connected to the Pressure regulator 378 is connected and the pressure regulator 378 is connected to a water saturator 382 and a collecting container 386 via lines 380 and 384. The collecting container 386 is connected to the permeation separator 390 according to the invention via a feed flow inlet line 388 which comprises a bypass line and a valve 406. The product or residue line 392 extends from the separator 390 and is divided into two lines, of which the line 393 is in connection with a consumption system 395 for dry air (ζ. B ₀ a container, a line or the like) and a control valve 394, and of which the lines 397 and 398 have flow control devices 396 and are connected to the inlet line 400 for the reflux or clarification flow. An external clarification tank 406 is connected to the clarification stream inlet line 400 via a line 408 which has a control valve 410. At the feed end, a consumer 404 for the clarifying agent or reflux agent exiting is connected to the separating device 390 via a line 402.

409847/0701

- 51-

When drying air according to the invention, compressed air flows from the storage container 372 through the line 376 and the pressure regulator 378 via the line 3SQ, the water saturator 382, through the line 384 into the excretion container 386 and then through the line 388 into the permeation separation column 390 according to FIG. Invention. The dispensed product flows through the lines 392, 393 and can flow through the valve 394 into the consumer device 395 for dry air. A portion of the product from the separation column 390 can be diverted to the desired external product flow by adjusting the valve 394 and adjusted to the appropriate clarifying agent flow for flowing out of the outlet line 392 through the line 397 and the valve 396 and via the lines 398 and 400 Are introduced into the .Permeationstrennapparat, passed in countercurrent through the space between the outer shell and the pipes and finally passed at the feed end through the line 402 and into the atmosphere for flow and dew point measurements, indicated in its entirety by the reference numeral 404. Can. Instead of a Rückflußstromklärmittels, _s having been brought, the flow control valve 410 and in.die line 400 and then introduced into the separation column 390, a coming of auf3en Klärmittel.von an outer tank 406 through the Leitung- 408, wherein he withdrawn from the S.peisegemisch

· '· ■ "" ■ ■ "■■■ · -'■" ■:. . - 52 '* - <■

409847/070 1: .. · ■ -. ..,., ·: - ■■ \ .----

2 ^ 27106

- sz -

Clarifies or removes components,

In illustrates apparatus according to 5C, as used for the embodiments, Uird Fig commercial air compressor tank combination is used, "The compressor used piston rings made of Teflon, and supplies clean air without any odor agent or Kompressorölverunreinigungan * The ^Pressure regulator 378 maintains the pressure of the feed fluid mixture to the desired setting. The Uasser- "saturator 382 and the discharge drum 386 with up to 100 'yes saturation of the compressed air at the desired pressure.'

Flit of line 388 is a bypass valve 406 for the Feed flow in connection, which samples the wet compressed air feed flow for dew point measurements at ambient pressure withdraws. The pressure at "the clarifier inlet 400 is slightly above atmospheric pressure in order to overcome the flow resistance Exiting clarifier is at 404 in a Sfcrömungs- and Dew point measuring device (not shown) removed. The measurements for the flow rates and the atmospheric dew point are carried out with test wet counters and dew beakers »

It is pointed out that it is in the device according to FIG Fig. 5C as well as all other designs listed here

409 847/07 0 1

ORIGINAL

Leadership forms, uo the Rückflussstrarn or Klärmittelstram below or above atmospheric pressure may be desirable in place of the flow control device or the valve 396 pressure reducing regulator and in the line 402 flow control devices to be provided.

Example 1 : The apparatus as in Fig. 5C was used. The permeation separator used contains a tube bundle, the tubes of which are made from ionic XR perfluorosulfonic acid "H +", have an outer diameter of 0.889 mm, an inner diameter of 0.635 mm and a wall thickness of 0.127 mm. The tube bundle is 304.8 mm long and

3 holds 62 pipes with a total internal volume of 6.0 cm.

The outer cover used is a tight-fitting glass that has an inside diameter of approximately 9.52 mm (3/8 ths englo inch) has. This device is called "XR 12 χ 62" designated. Initially, a wet air feed at a pressure of 2.81 at (40 psig) was used. the external product flow rate (D in,. Equation 1 as above discussed) is set to 0.041 space cfm and the clarifier flow rate (R in Equation 1 as discussed above) is set to different values over a period of four days with continuous operation.

The results obtained with the above procedure are shown in

409847/0701 -54-

Fig. 6A shows the flow rate (R of the effluent clarifier in room cfm above the dew point temperature of the effluent clarifier stream at Qat (0 psig) with the feed fluid mixture and product maintained at 2.8 at (40 psig) . Uie are shown, the lowest dew point Uird of the product, d. h "at -26.2 ⁰ C (-15 F) at a flow of the exiting clarifier uon about 0, Ü28 room CFRN obtained. Thus, the Uerte for ünn the clarifying agent flow (R ^ the external product flow rate (θ) and the pressure in the high pressure phase, ie the pressure of the wet air feed stream (n, ..) and the pressure in the reflux phase or low pressure phase

phase (Pj_ _o ) in equation (i) given above, the optimum ratio of the actual volumetric flow of clarifier flow to feed flow for this system is determined to be 1.5:

0.028 = (P / F) χ (0.028 + 0.041)

(40 + 14.7) /14.7 P / F = 1.5

Similar calculations are made, with others Flow rates (R) are used for the clarifier flow, as shown in Figure 6A. These results are shown in FIG. 6A via flow rates plotted on the abscissa. hexten of the exiting clarifier applied.

^ 09847/0701

23271

_e seen from Figure 6A, where a Klärrnittelstrom cfm greatly above the optimum, that is, higher than 0.028 "space, has been applied, the product has a slightly higher tratian dew point and therefore a slightly higher Uasserkonzen-. If a Klärmittelstrom with less than 0.028 space cfm or applied below the optimum, this has the effect that the product quickly rises in its Tou point temperature and so quickly becomes wetter, especially after the ratio P / F falls below 1. The reason for this can be seen from the dew point measurements of the exiting clarifying agent, which on the maximum value he would have at 15.9 C (60 F) or room temperature "karin. If the ratio P / F is less than 1, it can be seen that water vapor penetrates the pipes in the saturated high pressure feed phase and saturates the exiting clarifying agent flow and thereby stimulates a further passage, whereby water vapor through the pipes into the exiting clarifying agent stream. On the other hand, if the P / F ratio exceeds the unit, the exiting clarifying agent flow begins to have a lower partial pressure of water vapor than is present in the high-pressure feed means, so that a driving force, namely a concentration gradient for water vapor for the permeation at the entry point for the A feed stream mixture is present _o In this way the perm8ation separator is better utilized from end to end.

409847/070 1

A clarifying agent stream above the optimum, i.e. h "above of 0.028 space cfm, acts as an unnecessary additional Load on the dry system.

In further experiments, P / F is kept constant between 1.4 and 1.5, while the external product flow rate (D) is varied between 150 and 8,000 barely cm / min and the pressures for the feed stream mixture or for the high-pressure phase between 1.4 and 3 _? 3 at (20 and 90 psig) varied »The optimum P / F ratio for this permeation separator under these conditions is found in the range 1.4 to 1.6 using equation (i). The higher the water vapor reduction ratio, the drier the air product. High product flows result in low water vapor-air separations and low feed rates (ie low product flows) result in high separations. Under these conditions the greatest reduction in water vapor is in the product 29 _S 4 _? wherein a feed stream or product at 6.3 at (90 psig), a product flow rate uon 445 cm / min, a space of 118 Klärmittelströmungsrate CMVmin, a Uerhältnis P / F uon 1.52 and 15.9 ⁰ C (60 F) room temperature were used. In this operating case, the dew points were at 0 at the Speisernittelstrom, the product stream, and the exiting clarifier to -9.5 ° C (+ 15 ⁰ F) -42.8 ° C (-45 ⁰ F) and 9.5 ⁰ C

- 57 -

4098A7 / 0701

found.

3 Since the total internal volume of the ileal bundle is 6.0 cm, the total feed flow was 13.1 V / v / min (current volume of feed flow per volume of the pipe interior per minute). The food supply time is thus 6O / 13.1 = 4.6 seconds. The compressed air flows through the 304.8 mm long tube at a space velocity of 0.066 m / s (13.1 feet per minute). During the passage 97 % (= 100 (29.4 -i) / 29.4) of the water vapor is removed.

At the highest food rata carried out still obtained beneficial drying at 6.33 at (90 psig) with a moisture reduction of 4.4 in was given to the product. Compared to the lowest flow rate, the product and clarifier flows are equal 18.7 times larger and were at 8,330 and 2,310 cm / min. The dew points for the spoiler flow, the product flow and the effluent clarifier stream were -9.5 ° C (+ 14.5 ° F), -25.5 ° C (-13.9 ° F) b. + 9.5 ° C (+ 49.1 ° F).

Here the total supply current is 248 V / v / min, the delay time 0.24 seconds and the space velocity 1.26 m / sec. (248 feet per minute). Thus, in about 1/4 sec, 77 % (= 100 (4 ', 4 -i) / 4.4) of water was removed. The water equilibrium is 115 %, which shows that it is negligible

4098A7 / 0701

- 58 - ■

more water comes out than enters. This shows minor Measurement errors or that a constant state in three hours of operation under the above conditions is not possible have been achieved.

The above data clearly show that the air drying system according to the invention is highly effective, and produces very good results.

Example 2: A) In order to further check the improved results for air drying with increased tube length in the permeation column from Example 2, a

second permeation column (labeled XR 39.5 ' ¹ X 50) installed in series with a permeation column (XR 40''χ 50). The combination of a permeation column with a tube bundle of 50 tubes, each of which has a total length of 200.66 mm (? 9.5 inches), gives only good results, roughly twice the total product flow rate could now be obtained with the same product dew point. Dias corresponds to what can be expected when the columns are connected in parallel. It can be seen that the second column, which received the relatively dry exit stream of the first column, did not produce an equally large water vapor reduction

could.

- 59 -

409847/0701

Β) To ensure that the drying effect grab decreases when relatively dry feed streams used, the XR 39.5 "χ 50-5 column was used 1.4 at (20 psig), with a conductive dry supply current (dew point -30.6 C or -23 ° F) and a very dry food stream (tap point ~ 59 ° C or -74 ° F) is used became. Approximately 36 hours of operation were required constant state conditions with the conductive dry supply current (dew point -30.6 C or -23 ° F) to obtain. The reduction achieved was only 3.0 compared to 39 with a saturated feed stream. Both was at a feed flow rate of 192 V / V / min and obtained at 17.5 C (63 F) room temperature.

The reduction was measured again at lower feed flow rates of 74 V / V / min. The results are shown in Figure 13, which plots the water vapor pressure in an air feed stream (mm hg) below 1.4 at (20 psig) versus the reduction ratio. Figure 15 shows that the reduction decreases with einem- very dry feed stream to the unit, which means that the product is wet and the feed streams, the equilibrium of the Uasser- materials 160-172%, which are shown in Fig. 15, showed that more water came out than came in. This was giner permeation of room moisture through the outside

- 60 409847/0701. .

- Attributed to 60 tube made of polyethylene.

It can be seen from Fig. 15 that the ability to 'Water separation is less and less when the Partial pressure of the water vapor in a constant feed stream lowered at room temperature. 3e drier the semipermeable XR-Fimaterial (perfluorosulfonic acid) became so its permeability to water vapor became lower. It very long columns were therefore required for extreme product dryness. The XR-Fiaterial (perf luorsulfonic acid) however, showed good wettability so that it can effectively collect water vapor and high capacity

ο ο for drying gases down to -62.2 C (-00 F), including the

Range of commercially available adsorption dryers,

Example 5 1 In order to prevent the permeation of room moisture through the polyethylene outer sheath of the permeation column used in Example 2, a polyethylene cover or outer sheath was fitted around the entire permeation column as shown in FIG. 1B. This device setup was made with a very dry feed stream

α ο.

{Dew point -59 C or -74 F; and a feed stream flow rate of 74 V / v / min, a P / F ratio of 1.5 at room temperature of 17.5 C (63 F), with the supply current was pressurized to 1.4 at (20 psig). the

409847/070 1

23271D6

Cover was around a Pcrmsationsvorrichtung according to Fig. 1B fitted so that a concentric space between the outer cover and the outer shell of the permeation column is formed, and a small amount of product has passed through the concentric cover space. Fig. shows that with this construction the reduction ratio remains above 1, indicating that the permeation of Moisture in the room is eliminated by the polyethylene outer shell is. Fig. 15 shows that the use of the Clarifier-provided cover around the entire permeation column, the measured reductions from below 1 to 1.4 brings ;,

Example 4: The method and apparatus according to the invention were used to dry air. The same device structure as previously described was used. However, the permeation drying column was modified by changing the permeable material used in the tube bundle. In this operating example, the tube bundle used is made of dimethyl silicone, the tubes having an outer diameter of 1.65 mm (0.065 inch), an inner diameter of 0.635 mm (0.025 inch) and a wall thickness of 0.508 mm (0.020 inch) "Customs". The tube bundle is 1.34G mm (53 eng _o inches) long and had 38 tubes with a total internal volume in

- 62--

409847/0701

3
the pipes were 16.2 cm.

3. A permeation colonna was used in a second operating run with tubes made of nylon 101 with an outside diameter of 1.83 mm (0.072 inch) an inside diameter of 1.07 mm (0.042 inch) and a wall thickness of 0.331 mm (0.015 inch) was used. The tube bundle contained tubes 635 to 1371.6 mm (25 to 54 inches) in length and had a total internal volume

3
of 30.5 cm. The outer shell was made from heat-shrunk polyethylene that was ½ inch (927.1 mm) inside diameter.

The relevant data that were obtained are shown in Figure 1 for perfluorosulfanoic acid as in the examples 1 and 2 are used, for dimethyl silicone and for nylon 101. In Fig. 16 the reductions observed are above that current volumetric feed flow plotted per inner volume of the tube bundle, referred to as current l // l // min · This unit is proportional to the rate of the entering ufassar steam in the saturated feed stream. The ratio P / F is between 1.4 and 3,

- 63 -

409847/0701

Plit dimethyl silicone results in a large increase in the moisture absorption when operating at higher pressures. Hit the perfluorosulfonic acid material finds single Lich a small desirable effect with multiple pressures takes place.

In the double logarithmic graph in Figure 16, the results for the perfluorosulfonic acid material are straight lines, while those for silicone curve up sharply with reduced spoois current rate. Hit the 53 ^I! κ 33-dimethyl silicone column was the greatest reduction achieved 870. This product has a dew point of -67.7 C (-90 F). This corresponds to a removed water content of 99.09 % (= 100 (870 -1) / 870) through the column. The data in FIG. 16 demonstrate the operational efficiency of permeation columns according to the invention for drying compressed gases.

An extrapolation to lower feed flow rates is shown more clearly in FIG. 17, where the logarithm to base 10 of the reduction over the feed flow rate for wet air in a logarithmic hate rod is applied. For the vertical axis, 1.0 means that the reduction is 10, 2.0 means that the Reduction is 100, etc. The data is the same as

- 64 -

4 0 9 8 A 7/0 7 0 1

shown in FIG. For the silicone material, the curve is concave towards the top. At a feed rate of 1 V / V / min the reduction is 10. The estimated residual moisture in the product would be 1 ten millionth of the moisture in the wet feed stream.

The curves for the perfluorosulfonic acid material are in 16 concave downwards. The use of low feed rates to achieve extreme product dryness is not very effective on perfluorosulfonic acid material. A combination of columns made from perfluorosulfonic acid and Obviously, dimethyl silicone would be best for extremely low dew points at high flow rates. The perfluorosulfonic acid section would remove most of the moisture from the feed stream. The dimethyl silicone section, whose permeability for water vapor obviously does not decrease at low water degrees, the Reduce product moisture to extremely low values.

Example 5; In order to demonstrate the use of the method and apparatus according to the invention for separating carbon dioxide and oxygen as key or selection components from dry air, the following example was carried out. The apparatus construction used is that as described in Example "\ , with dimethyl silicone permeation material in the permeation column with 38 tubes

- 65 -

409847/070 1

1346.2 mm (53 inches) in length was used. Compressed air at a pressure of 5.55 at (79 psig) and at a flow rate of 2.1 V / v / min was introduced into the Introduced permeation column. The ratio of Clarifier flow to feed flow is 3.2. After three days

ο A product with a dew point of -67.7 C (-90 F) was obtained. Analysis of the product showed that carbon dioxide in the feed stream was reduced by a factor of 2 and oxygen in the feed stream was reduced by a factor of 1.06. The oxygen in the feed stream was 20.9 % and in the dry product 19.7 % by volume.

Example 6; The permeation separator from Example 5 was used to separate oxygen and carbon dioxide from air. Compressed air at a pressure of 5.54 at (79 psig) and a flow rate of 0.59 v / v / min was introduced into the column. A residence time in excess of 100 seconds was used. The actual clarifier stream / feed stream ratio that was used is a function of the location along the column and was 3.53 at the feed end and 0 at the product end. At a point which was 15 ρ of the column length away from the product end, the ratio P / F is 1.0. The analysis of the product shows an oxygen reduction by a factor of 1.28 from 20.9 / ό to 16.4 %. In the exiting clarifying agent stream, the oxygen content rose to 24.6 % . The reduction

409847/07 0 1 - 66 -.

- 66 of feed carbon dioxide per product was 8.2.

The data of this example show that for noticeable compositional changes in components, the less More penetrable than Uasser are, longer delivery times and / or longer columns should be used,

Example 7: A device was constructed as shown in FIG. A tall insulated container 122 held various amounts of a mixture of cracked ice and water which was agitated by a small stream of air which rose in bubbles from the floor (not shown). The permeation distillation column 126 was mounted vertically in the vessel to a point where a portion 128 of the product tail was submerged. The air feed flow was adjusted to 1.4 at (20 psig) through a supply line 130 with valves 132 and flowed through line 134 into a water saturator 136 and through a separator drum 138 into the tubes of the column, not shown. The dew point of the moist air feed stream was monitored by the sample valve 140 for the air feed stream. The moist air feed stream entered the tubes of the column via line 142. Dried air product was obtained from the tubes via line 144 at a pressure slightly below 1.4 at (20 peig). One valve 146 and one

409847/070 1

- 67 -

Flow control 148 in cooperation with a valve 150 and flow control 152 allowed something to withdraw from the dry product for external consumption and the rest of the dry product in countercurrent returned as clarifying fluid via line 154 at 0 at · The setting.; of the product and clarifying agent valves with wet meter records of the withdrawn product and the emerging clarifier made it possible to measure various Feed flow rates and ratios of the actual volumetric flow rates of the detergent to be used for supply current «. Dew point measurements at 0 at uurden either in the product line leading to the outside or - made in the inlet line for the clarifying agent

The column used in these experiments was 977.4 mm (38.5 narrow! · Inches) long and contained 50 parallel-connected Perfluorosulfonic acid polymer tubes. Each tube had dimensions 0.635 mm (0.025 inch) inside diameter and 0.127 mm (0.005 inch) wall thickness. The overall interior

3 volume of the pipes was ν = 15.5 cm · the feed flow rate was made from atmospheric wet meter measurements for the Product and the exiting clarifying agent flow are calculated. For a pressure of 1.4 at (20 psig) the current Volume of the feed stream per minute found if this

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409847/0701

- 60 -

was divided by the inner ualumen of the tubes a feed flow rate was found in printouts of the current volume of the feed flow per minute per volume of the pipes, abbreviated V / v / rnin. The residence time of the feed gas at a flow rate of 60 V / V / min was between 0.3 and 1.4 seconds.

The initial experiments with this device were repeated Measurements of the initial dew point reduction of the product, but with different feed flow rates, as shown in FIG. The 977.4 mm long column was initially set on a steady at room temperature Product dew point operated in the empty insulated container. The container was then filled with ice so that 419.1 mm (16.5 inches) of product end 128 of column 126 is immersed was. The product dew point was measured and found to be constant for several hours after immersion.

The extent of this initial drop in the product dew point according to FIG. 7 was approximately the same for a ratio υοη

ο 5: 1 of the supply flow rates at -35.9 C (-32.7 ° F) on average. This represents 90% of the mean -35.7 C (-36.3 ° F) change in ambient temperature (from room temperature to ⁰ ° C) around the 419.1 mm (16.5 inch) long product end of the Pillar.

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For a supply flow rate of 43 U / V / min, the product

o dew point initially due to the ice bath from -31.1 to -52.3 C (-24 to -62 F) where it was constant for 4.5 hours remained * After an operating time of six hours ^ the Product dew point to -5 ° C (-58 F).

Operation of the device was continued for the next 10 days to determine steady state results. In the first four days, the product dew point moved between -42.6 and -51.1 C (-44 and -SQ F) in the next two days, in which the immersion depth increased to 266.7 mm (10.5 inches). was decreased, the product dew point moved between -43.3 and -50 C (-46 and -58 F). During this time, the ice bath was held at 0 C (32 F) -! 3but the room temperature fluctuated by 1 ^ ST ⁰ C (3 ° F) by 2Q.5 ° C (69 ⁰ F) and the foodstuff varied by - 1 ₉ Sl ^c (3 ° F) around 27.2 C (49 F).

At the end of the six-day operation, the current violumetric ratio of clarifier to feed current (P / F) was increased. This was achieved by going over to a total reflux operation, ie the ratio P / F is ^p hi / ^p Lo ^{= 2} ' ³⁶ ' ^{The usntil 150 for} the product flowing out to the outside was closed and the atmospheric clarifier valve 146 was closed opened further to maintain the same feed rate, ie 42 V / V / min. The product dew point was reached in half a day

409847/07 01

- 70 -

stabilized and remained at -50.6 - 0.56 ° C (-59 - 1 ° F) for three days.

The increased ratio P / p u was chosen to be the Product dew point before daily changes in ambient temperature and the humidity level at the feeding end of the column. It is now an operation with the same State possible for studying the effect of the depth of immersion in the ice bath.

The initial immersion depth of 114.3 mm (4.5 inches) resulted in a temporary lowering of the product dew point (-20 C C-3S F). The effect of the immersion depth of the product and the column in the ice bath has now been investigated for different feed flow rates. The one feed jet rate was 42.6 rpm. These requests were made with buckets of total reflux (P / F = 2.36) in order to stabilize the product dew point. A steady state was reached in eight hours, with the product dew point UfFt dropping -11.1 C (-20 F) below that at an immersion depth of 0. Uährend five days of continuous operation uurden different immersion depths used showed Another three days of operation without immersion in that the Produkttaupunkt downward from -36 C at the beginning to -40 ⁰ C at the end (from -33 to -40 F) dropped slowly the operating run. This stems from

409847/0701 - 71 -

a slow symptom of hysteresis that occasionally in experiments with a material made of ferfluorosulfone- acid (XR) was found.

At the end of the operational run, all ice was removed and brought the entire column back to room temperature «The

° -> t ° r- \ product dew point showed an increase wan +7.8 u (+14 F) over the last constant state uert at room temperature. The initial and the final transition can be explained by the perfluorosulfonic acid material used, which increased and decreased its water uptake by cooling and heating the product end of the column. Enlarged water intake in the cooled section clearly shows an army with an enlarged water transport across the pipe walls.

Referring to Fig. 8, the critical value for this became estimated the extent to which the product end of the column must be immersed in the ice bath in order to achieve a maximum 'To achieve an effect on the drying of the feed stream. The values in this diagram indicate values with constant state, which show that the product dew points reached a minimum when about half the column was immersed in the ice bath. The optimum at an immersion depth of half the length of the column

- 72 -

409 8 kl / 0701

232710S

regardless of the feed flow rate in an area v / on 5: 1. The optimum at half the length also depends not of the two P / F ratios for the clarifying agent flow to the feed stream that were used. However, the extent of the dew point reduction achieved depends by soaking in ice up to about half the length of the column from the feed flow rate and from that Ratio P / F of clarifying agent to feed agent, as shown in Fig. 8 and in the following table:

Feed P / F product dew point improvement rate

none _with

Cooling cooling

200 V / v / min 2.36 -20.3 ° _C -29 ⁰ C -8.7 ° C (-15.5 ⁰ F)

^, 5 ° F) (-20 ^b F)

42 1.5 -32.3 (-26) -44 (-47) -11.7 (-21)

42.6 2.36 -37.0 (-36) -51.8 (-61) -14 (-25)

An analysis of this data shows that if more than half of the column is immersed, the product dew point begins to increase. Uenn the entire column in the ice bath is immersed, the product dew point rises to that of the ice bath. Liquid water would then be in the Collect column. Hit a full immersion would

ο
the exiting clarifier, saturated at 0 C, can mathematically remove only 59% of the entering water. In these conditions the system would look like a partial

409847/0701

- 73 -

self-clearing cold separators work, which is a condition is to be avoided.

This example therefore shows that no more than half of the column is immersed at its product end should, otherwise the maximum achievable lowering of the dew point begins to decrease.

An experiment was made to show that much lower dew points can be achieved by cooling. In this experiment two columns with 50 tubes were used one 1,828.8 mm (72 inches) long and the other 1,016.0 mm (40 inches!) long. The latter is shorter Column had a 609.6 ram (20 englo inch) long cooling zone, measured from the end of the product. This zone was set to -16.1 C

ο »
+3 F) chilled if chilling was applied * Avg

this technique made it possible to reduce the dew point by 14.4 C (26 F) for very high supply current dew points, such as shown in Fig. 8A.

Example 8: A drying experiment was carried out with wet benzene which was saturated with water at 37.2 C (99 F). It held 860 per cent of water. A 1016 mm (40 inch) long column of perfluorosulfonic acid polymer (XR) tubes was used, with 50 such tubes being placed in the column. Wet benzene at two flow rates of 15 and 45 cm / min was added to 40 weight-

409847/0701 -

- 74 -

promill (English 40 ut.ppm) with a clarifying agent dry nitrogen with a throughput of 3,630 cm / min at 0 at. No benzene odor for the exiting Clarifying agent flow detected. The water reduction obtained was 860/40 = 24. The residual water in the dry liquid benzene product uar etua equal to the proportion of water in an equal volume of room air,

The current volurnetric ratios of clarifier flow to edible flow rate 82.5 and 242. These high P / F ratios are necessary, ueil in the Benzene liquid dissolved water vapor by 50 to 30 times more than in the vapor equilibrium space above the liquid compressed uurde. The bulk density of water molecules in the liquid is 15 to 30 times that in the vapor equilibrium space. This compression is a function of the temperature and the type of immiscible liquid.

Example 9; This example shows the effect of heating the feed end of the column on drying flow mixes with high temperature dew points and an immiscible water content and also an entrained water content. A permeation distillation column for a test stream of high dew point gas

- 75 409847 / 07G1

was used in an experimental setup as in 9 shown.

Room air was passed through the system via line 156 a vacuum pump 153 sucked. The air stream was made of perfluorosulfonic acid polymer prior to entering tubes 162 (XR), which were arranged within the outer shell 160, initially through a sealed water pot blown, which was placed on a hot plate 156 maintained at a prescribed temperature by means of a thermostat 168 (Variac) was held. A plastic sieve 170 was used to prevent a spray from building up in the vapor space. A thermometer 172,

which dipped into the steam room measured the approximate Saturation temperature of the feed air. A wet meter 144 located at the air inlet measured the feed air flow rate. An uninsulated column was placed close to the pot 164.

A rotary rotary knife 176 in line 178, which is connected to diß Pipes of the outer shell 160 was connected to the product end, gave visual information about the product flow to the Dew cup 180, where its dew point was measured by the thermometer. The pressure in the dew cup was about 0.035 at (0.5 psi) below atmospheric pressure

409847/0701

a small pressure drop in the pipes. When operating with total reflux, all dry product was over line 184 into the envelope as a countercurrent clarifier via clarifier valve 186 and the Flow control device 138 returned. After this The effluent exited the column at a vacuum of about 0.802 atm (27 inches of mercury) line 189 into the vacuum pump through a separator drum and a filter (not shown). The heater 190 shown in FIG. 1 was used in later experiments.

An alternative arrangement, shown in Fig. 10, u was used room air as a clarifier. This uurde measured by a rotary lathe 192 and by a Clarifier valve 194 and a flow control device 196 are metered. Vacuum gauges 198 and 200 measured the inlet bzu. Outlet clarifier pressures. In the clarifying agent flow passing through the envelope 202 there is a pressure drop of about 0.05 to 0.134 atm (1.5 to 4 inches of mercury) present. With this arrangement this was done under ambient pressure Standing product is withdrawn from the dew cup 204 directly into the vacuum pump via the line 206. Of the Product flow was metered through product valve 208 and flow control device 210. The thermometer

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409847/0701

212 measured the dew point of the pipe 201 in the outer shell 202 leaking product.

During operation, the flow was started and the feed flow saturator on the. desired temperature in the same Ueise as described for Fig. 9, brought. the The temperature was kept constant until the product dewpoints were measured which were no longer subject to any further change.

Figure 11 is a graph showing the drying of supersaturated feed streams with room air using the apparatus described for Figures 9 and 1Q. The results are shown for a 965.2 mm (38 inch) long column with 47 tubes each having an inside diameter of 0.635 mm (0.025 inch) and a wall thickness of 0.127 mm (0.005 inch). The tubes were made of perfluorosulfonic acid polymer (XR). Both modes of operation were used, a total backflow (self-clarification, Fig. 9) and a clarification with room air (Fig. 10) the latter used a flow of room air (dew point -2.2 ^± 1.66 ° C (28 ± 3 ° F) ), which was equal to twice the product flow. Both were measured under room conditions.

- 78 409847/0701

With a dew point of the supply current of about 57.3 C. (135 F) the product dew point began to rise sharply. At higher dew points of the sewage flow, the product dew rose point to saturation at room temperature. The dew points determined in the rising part of the curves in FIG are unsure you wandered between the by the dashed lines connected values. The ball lathe knife for the product occasionally suggested what ginen momentary Indicated increase in resistance to product flow. It was concluded that in some of the pipes Droplets of liquid water had formed and a moving product dew point indicated this phenomenon. water began to break through the system.

Surprisingly, another phenomenon was observed during this experiment. When the entire length of the indoor air was exposed, had the one located near the hot water saturator Infeed almost the same temperature. However, the column temperature dropped towards the end of the product and walked over a cold zone below room temperature. The cold zone suddenly ended at a special point along the The column and the rest of the column were at room temperature. The f'litteluert from several measurements for the distance of the Cold zone boundary from the hot end of the food was re-usable within about 25.4 mm (1 inch) "

- 79 -

409847/0701

Operation of the entire system (pot and column) at room temperature showed no such cold zone. Only uann If the supply current was saturated at a dew point higher than room temperature, the cold zone appeared. The higher the saturation temperature of the feed stream, the further along the column the cold zone extended.

If the border of the cold zone extends to 25.4 or 50.8 mm (1 or 2 inches) across the center of the 965.2 mm (38 inches) Inch) long column, the product dew point began to rise sharply. This took place at a dew point

ο ο
of the feed current of 57.3 C (135 F) took place, which indicated that the water breakdown was imminent. The water breakthrough took place at higher dew points of the feed stream. The cold zone boundary extended to the end of the product and the product dew point was close to room temperature. The conclusion from these observations was that the usable drying capacity of the column was reached when the cold zone front was about half the length of the permeation distillation column reached.

Both modes of operation showed this phenomenon, both the total reflux, as well as clarification with room air. Both could do satisfactorily with feed streams with a dew point handled at 57.3 ° C (135 ° F). Zuei under-

-BO-

409847/0701

different Spoisostron rates at total reflux, from 47 and 91 V / j / min, also found their limit in one Dew point of the supply current of about 57.3 C (135 ° F) “In all cases with the 965.2 mm (38 inch) long column marked the arrival of the cold zone front at the Ride of the Column the beginning of the sharp rise in the product dew point,

A longer column was then used and good results have been obtained using a column 1752.6 mm (69 inches) in length with 50 tubes. A satisfactory product dryness zuischen -37.2 and -32.2 C (-35 F ⁰ -26 and F) was obtained for Speisestromtaupunkte in the range between room temperature up to 74 C (165 F). At this temperature the cold front extended to about the middle of the longer column. Feed streams with dew points of more than 74 ⁰ C (165 F) caused a strong water breakdown, as shown in FIG.

A heater 190, Fig. 9, was installed and covered around the inlet ports and around the feed end of the column the first 355.6 mm (14 inches) of the 17.52.6 mm (69 inches) long column towards its product end. A thermocouple, which is at a distance of 101.6 mm

- 81 -

409847/0701

- G1 -

(4 inches) was arranged by a Gardsman temperature controller. This device switched the electric heating on and off to the set aJert to maintain. The temperature at the thermocouple varied between 84 and 36.3 ° C (183 and 109 F). the The mean continuous drive power used was 37 watts Environment discharged because the tightly wound band heater was not insulated.

When the heating was in the gearbox, slightly higher product dew points were observed at relay current dew points up to 74 C (165 F). No meGbaro cold zone occurred in this area. A cold front was found at feed current dew points of 82 and SB ⁰ C (10 and 190 ° F). Successful drying to -27.2 C (-17 F) was achieved at a feed current dew point of 88 C (190 F), as shown in FIG. The start of water breakdown was estimated for a feed current dew point of about 89.5 C (193 F) with the heater, compared to 74.3 ° C (165 F) without it.

The continuous drying of a feed stream with a dew point of 87.7 ° C (19O ° F) to a Produkttaupunkt of -27.2 ⁰ C (-17 ⁰ F) is an unexpected success. The wet feed stream entering the column contained 63.5 volume percent water vapor. The water in the dry

409847/0701

Product exiting the column was only 0.05 l / olumon percent. The ratio of this value, with Reduction is 1270. 1/127O of the water im Feed stream was shown in the product. The rest was discharged by the heated clarifier

No continuing collection of 'Jasser was found in the Permeation-Esbillations-Shell took place and Uasser collected in the inlet and outlet separators of the vacuum pump. Automatic extractors for these separators are available required for continuous operation of the system.

All of these results are plotted graphically in FIGS. 11, 12 and 13. Observation since (3 a water leakage Imminent, when the cold front reaches the ridges of the pillar, is significant in the first Embodiment it showed the advantage of an applied Cold zone around the product end of the column, with an immersion depth caused the column to operate unfavorably beyond its half. In this embodiment showed an extension of the self-generated cold zone beyond the center of the column also marks the beginning of the water breakthrough and from unfavorable results. Thus there is a surprising and unexplained temperature symmetry around the Rides of the permeation distillation column.

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409847/0701

Example 10: In this example, the technical effects of a water permeation distillation process were observed in which a purge stream of dry gas in the gas stream is used to induce the evaporation and cooling of a fluid containing water which is contained in a zona is heated in the hitts of the column.

Referring to Figure 4, the _o following example was performed to find out how much 'Jasser can uerden distilled. A permeation distillation column 2540 mm (100 inches) in length was used which had 45 tubes of merfluorosulfonic acid polymer hydrogen. The tube was 0.635 mm (0.025 inches) inside diameter and 0.127 mm (0.005 inches) thick. The tightly fitted stainless steel shell was 12.7 mm (0.5 inches) in diameter. A ribbon heater 58 was tightly wrapped around the envelope and in the crevice of the column. It extended 8 inches (203.2 mm) from each side of the bottom of the column,

A thermocouple 62 measured the temperature at the center and signaled a Gardsmen temperature control device (thermostat) 66 when the heating is electrically on or switched off and rnui3te to the set temperature

- 04 -

409847/0701

to keep. Thermocouples 70 and 72 were also at the Sheath 50.8 rom (2 inches) beyond the ends of the heater Installed. The entire column was thermally insulated

The column was placed at a 50 ° angle to the vertical to remove air pockets from the envelope by the upward flow of the feed stream. The circulation of the water feed flow became maintained by a sump pump GB in a water bucket. The water exiting the envelope dripped back into the bucket, and its rate of leakage is measured could. A water flow valve 75 held the desired one Circulation rate and thermocouples 74 and 76 measured inlet and outlet water temperatures on a multi-point temperature indicator.

Provided a source of dry air at 1.4 at (20 psig) the clarifying air and a clarifying agent valve 86 maintained the desired pressure in the pipes 56 to create a flow of sewage gas in the Maintain countercurrent. At the outlet of the cleaning agent A measuring beaker 84 collected the water condensate from the column. A wet meter at this stable measured the sewage air currents Frequent attempts have been made to find the To secure leak tightness of the envelope and the tubular column. Thermocouples 88 and 90 measured the temperatures of the sewage air

- 85 -

409847/0701

- 85 currents at the inlet bzu. Outlet.

In operation, the circulating water with the device set to room temperature. Its flow rate was set at 20 to 70 cm / min. EinlafJ-Druck the clarification air was adjusted to values between 0.14 and 0.7 at (4 to 10 psig). The operational sequence u was observed to ensure that no liquid water appeared in the exiting stream of clarifying air and that no air bubbles were present in the exiting water,

After the heating was turned on, water condensate soon began to appear in the effluent clarifying agent stream. After four or five minutes of operation started the temperature control with cyclical switching on and off the heater to keep the set point slightly less than 212 ° F (100 ° C). Within half an hour that reached! / experienced a steady one Operating condition. The measured temperature and the flow rates remained constant »Typical operating values for an operational run with the 2540 mm (i00 engl. Inch) long columns are shown in the top half of Table I. The flow rate for the distilled water condensate, The rate of uelches with the exiting clarifying air was 5.3 cm / min. To water at this flow rate to distill, would normally require 206 watts,

4098A7 / 0701 "■ ^B6 ""

if its mean latent heat of evaporation of water of L = 560 cal / grm is taken as a basis. Medium slide The power from the heater was 103 watts. Consequently, distillation became water in this novel permeation distillation process accomplished with half (= 103/206) of normal heat. The gas office number is 2.0.

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409847/070 1

TABEL

H column (Fig. 4)

XR 1QQ "χ 45
Flow:

Temperature sin
the end

Clarifying air

Circulating

Uasser

0.21 RRCFH

22.2G (72.5 F)

24.4 ⁰ C (76 ⁰ F)

26.2 ⁰ C ( ⁰ F)

46.6 ° C (116 ⁰ F)

σ heat loss:

to the circulating water

j ^ by isolation

^ countable losses

ο Net heat to evaporate water

^ H Evaporator: Na condenser (Fig. 5) . ', XR 31 "χ 50: XR 29" χ •' Flow 0.61 RMCFM '63 cm ° / min

Temperature

the end

26. 6 ^L

(8i * f;

36.1 ^c

(97 ° f;

Warmth:

for circulating water through insulation

Total heat losses that can be counted in the sewage air exiting Net heat to evaporate the water

(the end)

36.7 ⁰ C (9S ⁰ F)

45.5 ⁰ C (114 ⁰ F)

Heating zone

83.3 C
(132 ⁰ F) , 5 ⁰ C
36 ⁰ F) 85 watt 60 12th watt 70 watt 33

Water condensate effect

Reduced performance number

103 watts 5.3 _cm 3 / min (medium)

1070 cal / min 5.Q5 cmVmin ** '*

72.7 ⁰ C (162QF)

89.5 ⁰ C (193 ⁰ F)

cal / min

636 cal / min cal / min

* Middle point temp. 99 ° p m contains 0.55 cm ^ / _m - _n rV ·· ^u ~ · ' \

/ mm. Humidity as steam in the emerging clarifier

equivalent to

206 Uatt

2.0 gross

206 watt 6o25 net I.
CO
-O I. 2830 cal /
min 2o64 Gross

2830 cal / min 6.52 net

Uonn made corrections for the countable heat losses the net effect factor is 6.25. This means, daG i / 6.25 of the normal screen in the current case was used to distill the water.

Most of the heat losses that can be counted occur in the exiting circulating water, the feed water with a flow rate of 47.3 (= 42.0 + 5.3) entered the Column at 26.2 C (79 ° F) and was raised to about 99 C (21 ° F) heated up as it passed through the heating zone.

In the heating zone and in the evaporation section

3,
5.3 cm / min evaporated by the sewage gas. In the dam-

ο
The Uasser was reduced to 46.6 ° C

(116 F) cooled to the temperature of the 42 cm / min flowing water reflux. The countable heat loss

ο α. for the total water temperature rise of 26.2 C (79 F; at 46.6 C (116 F) was equivalent to 60 Uatt. Hit one Isolation loss of 10 Uatts, the total countable heat losses amounted to 70 Uatts. The net heat for evaporation of the observed water condensate was 33 Uatt. The net effect number was 6.25.

ο ο In the evaporation zone the water of 99 C (210 F)

cooled to 46.6 ° C (116 ° F). According to equation (3), 4.1 cm / min were evaporated to cause this observed cooling

- 89 -

£ 09847/0701

using L = 5Θ0 cal / grm. Consequently

3
the evaporator delivered 4.1 cm / min and the heated one

3,
Zone added 1.2 cm / min to generate the observed ge

3.

velvet distillates added at 5.3 cm / min in the clarifying effluent.

In the ideal case, the evaporation section should circulate there Cool water to its initial inlet temperature. The length of the evaporation section was evident insufficient to establish this ideal condition.

Results from other operational runs for an individual 2540 mm (10Q inches) long overall H-pillars are in 14 shown. The observed gross efficiency figures are between 1.5 and 2.0. The net effect numbers grow sharply from 2.5 to 6.25 when the flow rate for the water condensate is increased by a higher heating zone temperature. rature has been increased.

These results demonstrate the remarkable ability of a permeation distillation column with an average Haizzone for the distillation of water from liquids with less than the normal latent urine of evaporation. Since Perfluorsulfonsäurepolymsr is impermeable to most organic and inorganic vapors, Uasser

- 90 - ■

4 09847/0701 _rf

232710 8

containing mixtures of such constituents to be dried. The Uassereffluent can further Recirculated drying in discontinuous operation or a series of columns can be used for continuous drying to the desired moisture level be applied.

A run was carried out with a salt water feed stream containing 22.5 grams of sodium chloride per 1000 grams contained tapped water. This is roughly the middle one

Salt concentration of sea water. The flow rate of the

3.
Condensate was 2.8 cm / min with a flow rate of the

3
Salt water effluents of 31.5 cm / min. The effect numbers

were 1.2 gross and 3.0 net. The diamond-shaped measuring points in Fig. 14 indicate this operational run.

The condensate from this operating run tasted only slightly salty. From evaporation experiments it was estimated that the salt in the condensate was less than 1/10 of that in the feed stream. That salt is in The distilled condensate was surprisingly present as there were no leaks between the tubes and the shell were present.

In the condenser section of 2540 mm (100 inches) Long total H-column with a single tube was filled with liquid water

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2327-1Q6

on both sides of the tubes. On this condition the salt may have migrated slightly into the condensate be. In addition, some of the condensate may have flowed back into the feed stream, causing the distillation process short-circuited. In all permeation-distillation processes it is always desirable to have a thin liquid vapor phase on a surface of the permeable To have pipes. A shorter, more limited heating zone and an impermeable condensation section can enable the device to enhance.

Example 11: In accordance with these considerations, a new permeation distillation column was assembled and tested. The new column used separate sections with an external heating system for the circulation of the water (Fig. 5). From all other points of view it was the same as that which is described for FIG. The evaporation section 98 was 787.4 mm (81 inches) long and contained 50 tubes of perfluorosulfonic acid polymer in the hydrogen form (H). The condensation section was 100 µm (29 inches) long and contained 50 tubes of the same base stock but on the Sodium Sulphonate (Na) farm. The Na form, produced by ion exchange, among others from the others

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409847/070 1

23271

Experiments as being 1/5 to 1/10 times as permeable to Water as the sulfonic acid H form.

The external heater 10G for the circulation of water and others a hot water bath with a copper snake 108, a Immersion heater 110, a thermocouple 112 for the temperature controller 114, and an air bubble generator 111 used to stir the bath. The controller 114 switched the electric heater 110 on and off to the Set to maintain the temperature in the bath. Thermocouples 120 and 122 near the sheath sections 98 and 100 measured the inlet and outlet temperatures of the circulating water as shown in FIG. His Flow measurement combined with its temperature rise in the hot bath allowed a narrow determination of the heat input in the column. Lower insulation losses for the column of approximately 3 Uatt were achieved with this new arrangement obtain.

A typical operation with this H: Na — evaporator— Condenser combination is in the lower half of Table I. shown. The flow rate for the distilled water condensate, which together with the clarifier effluent emerged was 5.05 cm / min. With a value of L = 560 cal / grm, this amount of condensate would normally be Require 2830 cal / min. The total heat input to the

- 93 -

409847/0701

The column from the hot water heating bath was 1070/2830 = 1 / 2.64 the normal evaporation heat. The observed gross action factor uar 2.64.

After corrections for the countable heat losses such as according to table I the net effect factor was 6.52. This assists the operability of the assembled column in this new type of permeation distillation process. Water can evaporate with much less than the normal heat distilled.

The greatest heat loss in the assembled column was again in the effluent of the circulating water. The circulating water became in the evaporation zone cooled from 89.5 ° C (193 ° F) to 45.5 ° C (114 ° F) by the clarifier-induced evaporation through the tube walls. According to equation (j) should be 5.14 cm / min as wet be correct for the observed cooling. Since 5.05 cm / min was actually obtained, this is obvious Evaluates the validity of the equation and the use of L = 550 cal / grm for the mean latent heat of evaporation by Uasser. The fact that the circulating water entered the column at 36.1 ° C (37 F) and at 45.5 C (114 ° F) indicates the evaporative section not long enough to let the circulating water on its

- 94 -

4098 4 7/0701

- 94 inlet temperature to cool down.

Results with other operational runs with the compound H: Na columns are shown in FIG. The watched Gross impact numbers were between 2.5 and 3.0. the The net efficiency increased sharply from 3.0 to 6.5 as the flow rate for the water condensate increased uurde. The composite column appeared to work better than the total H single column because it was taller Gross coefficient of action. However, after the countable thermal losses have been corrected, including the net coefficient of action the same for both types of columns, as shown in FIG.

A completely impermeable Teflon consendor, 3.05 m (10 feet) long with a single tube of 6.35 mm (1/4 inch) diameter in a 12.7 mm sleeve (1/2 inch) diameter was used experimentally. The results with it were no better than with the total H-single column, as shown in FIG.

Example 12: In order to investigate the transport of water from a liquid phase through a tube made of perfluorosulfonic acid polymer, an experimental set-up as shown in FIG. 18 was used. A bundle of 5T33 polymer pipes

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409847/070 1

uncovered, 876.3 mm (34.5 inches) in length and 49 tubes each having an inside diameter of 0.635 mm (0.025 inches) and a wall thickness of 0.127 mm (0.005 inches), u was immersed in an open water pot 501. The bundle had an outer surface of 11.61 dm (1.25 square feet) and had to be loaded by a weight in order to submerge. The open pot was kept at various temperatures by means of an electric heating plate 505 which was operated by a variac-
Device 507 (thermostat) was controlled. A source for
dry compressed air at 1.4 at (20 psig) was used for the clarifier. Its flow was through a
Flow controller 509 regulated. A pressure gauge 513 measured the inlet pressure of the dry clarifier required to force the air through the system. Most of the pressure drop occurred across the tube bundle.

Hot exiting air and water vapor from the tube bundle was passed through a serpentine 517 in the cold bath. Escaping condensate was collected in a measuring beaker 519. Air pressures from 0.35 to 1.055 at (5 to 15 psig) were used and the flow rate for the air was determined by connecting the condenser effluent to a test wet meter measured.

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409847/0701

There was no impact on the entire system at room temperature Condensate formed and the dry stream of sewage air entered saturated with 'jasser at room temperature. Uenn the pot was heated, condensate collected in the cup, as shown in FIG. At pot temperatures between 32.2 and 99 C (90 and 210 F) were flow rates for water condensate kept liquid up to 13.5 cm / min.

The highest flow rate for that withdrawn from the pot Condensate represented more than 500 Uatts of heat of evaporation. The heat transport transversely to the ends of the pipes exceeded 400 Uatt / 9.29 dm and it was difficult to keep the tap temperature keep constant. The horizontal bars in Fig. 19 represent the drop in pot temperature during the accumulation of condensate.

This flood vapor transport was both at 876.3 mm, and at 495.3 mm (34.5 and 19.5 inches) immersion length as shown in the upper curve in FIG.

Lower transport rates were obtained with an immersion length of 10.5 inches (266.7 ram) of the bundle. Obviously is a minimum length available for the bundle for maximum water transport

409847/0701

During the search described with Fig. 19 it was found that that at clarifier pressures below 2.1 at (3 psig) stagnant fractions of liquid water in several Pipes formed. These liquid parts blocked the flow of air through each tube. Clear mean pressures over 2.8 at (4 psig) uars are required and used to blow the plugs and prevent their re-formation. To maintain the vapor phase in all tubes, a pressure of at least 2.8 at (4 psig) for the clarifier required.

The effect of pressure and clarifier flow on condensate flow rate has been carefully examined. The pot

It was kept at an average temperature of 76 C ^ 169 F /. Flow rates for the condensate for different Clarifying agent pressures were measured and shown in Fig. 2Q shown. The flow rate for the water condensate uar im Result proportional to the clarifier inlet pressure up to about 0.246 at (3.5 psig). Above 0.246 at (3.5 psig) The condensate flow rate also increased very slowly with increasing clarifier pressures.

A calculation of the partial pressures of the one leaving the tube bundle The water vapor for each clarifier inlet pressure is shown in FIG. The calculation was based on the

- 98 -

409847/070 1

Results of the flow rates of condensate and sewage air. Figure 21 shows that at low clarifier flow rates, the effluent from the tube bundle had a constant partial pressure for water vapor of 311 mm Hg. This is the manual value for Jasser at 75.7 ⁰ C (17O F). The middle pot

O ⁰ N

temperature uar 76.1 C (169 Fj, It follows that up to
0.246 at (3.5 psig) clarifier pressure, the sewage gas
the tube bundle left saturated at pot temperature.

At higher clarifying air flow rates, the air offluent exiting the tube bundle was less saturated than at pot temperature. The dry stream of clarifying air breaks through without being completely saturated _o The discontinuity
in the curves in FIGS. 20 and 21 mark the separation between these two areas. The most effective
Benefit for the bundle of permeation tubes is obtained when the dew point for the one emerging from the tube bundle
Clarifier effluents below the water dew point in the
Pot lies. It is a driving force for permeation
present along the full length of the bundle. In addition, no condensate forms in the pipes, which the
Blocked flow through this. This case is analogous to
the desirable application of an actual volumetric flow ratio for clarifier to feed stream of
greater than 1 in a permeation distillation column, like

- 99 409847 / 07Q1

2327108

described in Example 1 and with Fig. GA, uo the dew point for the clarifying agent that escapes, it is less than that in the wet high pressure feed gas.

In the event that it is necessary to measure the steam pressure of the liquid or to create a gas flow with the same partial pressure of water as it is above the liquid in the pot, a low clarifier flow rate is used. This case is shown for low Klärmitteldrücke and flow rates in Figure 20 and 21 _o,

Example 13:. To investigate the same procedure under conditions where the vapor pressure of water in the water mixture is above atmospheric pressure, a closed system was used

An ordinary household pressure pot was found to be ideal for Press up to 1, Q5 at (15 ps.ig) found. The lid of one National — Presto 4 qt — Druckkachers was using a thermometer and a pressure gauge. Two through connections were made to the headers of one loose Connected bundle of permeation tubes. The bundle was 723.90 mm (28.5 inches) long and contained 49 tubes, each of which has an inner diameter of 0.635 mm (0.025 inch) and a wall thickness of 0.127 mm (0.005

409847/0701 - ioo -

angl. Inches). The Hatsrial uar dia sodium sulfonate farm van dem Perfluarsulfonsäurepalymer, uas for water as is known to be less permeable than the one previously used Hydrogen form.

With the structure according to FIG. 18 and pot temperatures of 100 to 114 ° C (212 to 237 ° F) or the flow rate for Uasserkondsnsat with clarifying air larger than without, uie shown in Fig. 22. With clear air, the throughputs were in the range of 2.9 to 5.5 cm / min. Without clarification air, condensate was

rates - from 0 to 4.5 cm / min above the same temperature or Preserved pot pressure area. In all cases in Fig. 22, application of an air purifying agent increased throughput of the 'Jasser condensate.

Without a clarifier, the condensate flow rate is the same, whether the bundle is immersed in the liquid or whether it is that it is attached to a hanger in the steam room. The vapor space has been vented to remove residual air. Hestluft in the steam room would hinder the water transport through the pipes.

The quality of the condensate in all experiments was comparable to that of commercial distilled water. ! Medium hard Tap water was used in the pot. Salts

- 101 409847/0701

in which tap water are not transported through the pipes, provided that a surface is kept entirely in the vapor phase. This resulted in the advantage of a sewage gas of sufficient space around the vapor phase in the pipes maintain.

Figure 23 shows a summary of the results of the clarifier induced surge data for Uasser. The water condensate, which was recovered in the condenser is proportional to the partial pressure of the water in the pot of 50 mm Hg to 1.6 atmospheres. Of the two different Codifications of the perfluorosulfonic acid polymer used transported the preferred acid (H-) rodification for example five times more water than sodium sulfonate (Na) iodification. The two modifications can be exchanged for a suitable ion exchanger · The equivalent weight des [material was about 1200, a range of equivalent weights between 950 and 1350 can be used for this Method can be used, the former having the highest permeability to water,

Example 14: In this example the procedure for drying sulfuric acid was used. The apparatus was similar to that in FIG.

- 102 409 847/07 0 1

Matched lid covered uar, the lid became the atmosphere vented via a cold water condenser, at uelchen connected a three-way vent pipe. The combination vent system maintained atmospheric pressure in the kettle and prevented leakage v / of UassGr and acid vapors through the ventilation system. The venting material pipe prevented ambient air vapor at the entrance to the boiler,

The glass kettle is about 2.272 l (2 quart.) A 1016 mm filled with 15 percent by weight of sulfuric acid 40 inch long bundle of 50 perfluorosulfonic acid polymer tubes (H) u was charged for immersion in the liquid acid. Connections to each end of the Bundles were made through the lid. Batched nitrogen at 0.703 at (10 psig) was used for the clarifier flow of 0.9 space cfm used. The water vapor removed from the acid by the clarifier was in a large Cold water condenser condensed and measured after it had collected in a measuring beaker.

The acid was heated up and kept at 95.degree. The other

³ /

catchable condensate flow rate was 12 cm / min for

15 weight percent acid. The condensate flow rate increased gradually decreased to 6 cm / min when the acid strength reached 45 weight percent, at which point the trial

409847/0701 "^103"

ended uurde. Manual of water vapor pressure, recorded

o wear übar schuefelsäure boi 20 C show a 2: 1 l / er— ratio won water vapor pressures between 15 to 45 percent by weight Acid. Dar observed water condanate throughput confirmed this relationship, "The falling of the condensate" durchsatz.es when the acid was dried and confirmed also that the water transport in this process is proportional to the 'water vapor pressure above the water containing Liquid is.

The water condensate distilled from the acid had one PH value of 5.0. It showed no sulfation in a barium chloride test. It tasted like distilled water. A liquid containing water was applied to this process. sulfuric acid partial through this new type of permeation drying rides.

If in these documents the absolute sizes for jeueils numerals representing the same size, of which one in the German system of measurement and the other behind it in the Expression in brackets is given in the English system of measurement, deviates from each other, the one given in the English PiaOsystern applies 'Jart.

~ Patent claims -

- 1 04 -

409847/0701

Claims (1)

Claims 1. Device for separating one or more keys - components from a flow component flow mixture, characterized by a permeable, preferably polymeric Hollow member with walls defining interior channels that are selectively permeable to those key components are to be removed from the flow mixture, an outer shell in which the hollow member can be enclosed, the outer shell being arranged such that the inner walls of the outer shell are arranged in close proximity to the walls of the hollow member, so that around the and a passage space through which a fluid is formed is formed between the hollow member and the outer shell can be passed through in contact with the walls of the hollow member, first feed flow inlet means in communication with one end of the inner channels of the hollow member, first flow outlet means which are in communication with the inner channels of the hollow member and are arranged at an end of the inner channels opposite the feed flow inlet means,
second flow inlet means, which with the through the 409847/0701 _ ₁₀₅ _ Outer shell and the hollow member formed passage space are in communication and through which a reflux fluid or clarifying fluid can be introduced into them, with the flow inlet means being passed are arranged near the first flow outlet means or at the end having them, second flow outlet means connected to the passage space formed by the outer shell and the hollow member communicate and close to the first spa outlet inlet means or are arranged at the end having them, and first conduit means for connecting the first flow outlet means to the second flow inlet means. 2, device according to claim 1, characterized by a arranged in the line means pressure control device to maintain the pressure in the reflux or KlMrströmung, which is less than the pressure in the feed flow, wherein preferably a part of the the residue stream exiting the first flow outlet means is recyclable as a reflux stream. 3. Apparatus according to claim 1, characterized in that the outer clarifying flow inlet means are arranged in connection with the second flow inlet means » 40984 7/070 1 - ioe - 4. Apparatus according to claim 1, characterized by a cover which surrounds the outer cover and fits tightly on it, uodurch an open space to mix the cover and the Auöenhülla is formed, and by second conduit means which are arranged near the residue flow end and in connection with the open space are provided which and the outer shell is limited by the cover, and which are connected either to an outer Klärmittelquelle or the Rückstandsströmungauslaßmittel or RückflußeinlaOmittel, and through outlets, which are arranged in close proximity to the feed flow inlet means ₀ 5. Apparatus according to claim 1, characterized in that the hollow member aufueist a plurality of tubes and as Tube bundle is formed, wherein the tubes of the tube bundle have a greater length than their diameter amounts to. 6. Apparatus according to claim 5, characterized in that the tube bundle is bent, wound or turned or the like. v / expires. 7. Apparatus according to claim 1, characterized by an sealing means disposed at each end of the hollow member 409847/0701 - 107 - for sealing the inner channels of the hollow member against the passage space between the hollow member and the inner walls of the outer shell. 8. Device, characterized by one or more permeable polymeric hollow members with walls that form inner channels and are selectively permeable to water, by an external device, in u / elcher the hollow links can be enclosed and which around the hollow members a passage space is formed, with the outer inlet direction a fluid can be received in contact with the walls of the hollow member, by first feed flow inlet means, which with a The end of the inner channels of the hollow member are connected to its feeding end, by first flow outlet means communicating with the inner channels of the hollow member and at one the feed flow inlet means are disposed opposite end, and by a pressure control device through which a flow either within the hollow member or in the External device is controllable or both, as well as by one arranged in close proximity to the external device Control device «! - 103 - 409847/0701 9. Apparatus according to claim 1 or 3, characterized in that that the polymoric hollow link is a solid one Perfluorocarbon polymer is what side groups from either sulfansmure, sulfonate or sulfonic acid and having julfonate. 10. Device characterized by one or more permeable polymeric hollow members with walls, the inner cannula and are selective / parmeable for water, an outer shell in which the hollow member can be enclosed is, wherein the .Outer shell is arranged such that the inner walls of the outer shell and the hollow member a through- delimit the passage around the hollow link and the shell, and a self-clearing flow means through the outer envelope can be passed through in contact with the Ujinden of the hollow member is, through first flow inlet means connected to one end of the The inner channels of the hollow glial are connected at the feeding end, by first flow outlet means communicating with the inner channels of the hollow member and at one the end opposite the feed inlet means are arranged, by second flow inlet means which communicate with the passage space between the outer shell and the hollow member and through which a reflux or clarification 409847 / 070-1 - 109 - fluid can be passed through, whereby.die second Flow inlet means near the product outlet means or located at the end containing them, through flow outlet means connected to the passage space communicating between the outer shell and the tube and near the feed flow inlet means or at the end having them, by conduit means for connecting the first flow outlet means with the second flow inlet means, through flow control devices in the line means for returning the feed flow as a reflux flow through the second flow inlet means and into the passageway between the outer shell and the hollow member are arranged in the counterflow to the feed flow, by temperature control devices which are either in close proximity to or in contact with the outer shell predetermined zones along the outer shell for causing a difference in temperature to a part of the outer shell are arranged on the temperature of the remaining part of the outer shell. 11. Device, characterized by one or more permeable polymeric hollow members, with walls defining interior channels that are selectively permeable to water are, 409847/0701 " ¹¹ °" by an outer shell in which the hollow member or the hollow members can be connected bzu, are, the Outer shell is arranged such that through the inner walls the outer shell and the hollow member a passage space around the hollow member and the outer shell for implementation a side clarifying fluid is formed in contact with the walls of the hollow member, by first flow inlet means, which are in connection stand with one end of the inner channel of the hollow member at its feeding end, by first flow outlet means which are in connection stand with the inner channel of the hollow member and are arranged at an end opposite the feed inlet means are , by second flow inlet means which are in communication stand with the passage space between the outer shell and the hollow member and through which a backflow - or Clarifying fluid can be passed through, the second flow inlet means near the product outlet means or are arranged at the end exhibiting them, second flow outlet means in communication with stand the passage space between the outer shell and the hollow member and close to the feed inlet means or on the these ends are arranged, 409847/0701 - 111 - first conduit included, which are connected to the local flow inlet means for discharging the dry product for external use, by second conduit means connected to the second flow inlet means, through flow control devices which, in the second conduit means to maintain the flow, use the air flow means between the outer shell .and the hollow member are arranged in the countercurrent to the Spaisestrorn , ■■ '.. ■ - " by temperature control devices either in close proximity to or in contact with the outer shell at predetermined zones along the AuiSanhülle zum -Bowirken a difference in temperature at one part of the outer envelope from the temperature at the remaining one Part of the storage envelope. 12. Device, characterized by a permeable polymeric Hollow member with walls that form internal channels and are selectively permeable to water, by an outer shell in which the hollow member can be enclosed and which is arranged such that The inner walls of the outer shell and the hollow member provide a passage space around the hollow member and the outer shell form through which a self-clearing fluid 409847/0 7 01 -112- 2327108 can be passed through in contact with the walls of the hollow member is, by first flow inlet means which are in communication with one end of the inner channel of the hollow member at the Standing at the end of the meal, by first flow outlet means, uelche in communication stand with the inner channel of the hollow member at one end which is opposite the feed inlet means, by second flow inlet means, uelche in connection with the passage space between the outer shell and the Stand hollow member and a reflux or clarifying fluid can be passed through uelche, the second Flow inlet means close to the product outlet means or are arranged at the end exhibiting them, by second flow outlet means which are in communication with the passage space between the outer shell and the Hollow member stand and close to the feed stream inlet center or at the end having these, first conduit means for connecting the first flow outlet means with the second flow inlet means, a flow control device, which in the first Conduit means for causing a portion of the product stream to flow as a reflux stream through the second - 113 - 409847/0701 23271 Flow inlet center and into the passage space between the outer shell and the hollow member in countercurrent to the Feed stream is arranged, through second conduit center, the one with the first "flow outlet means for removing a desired portion of the dry product for external use are, Temperature control devices, dia either in denser Proximity to or in contact with the outer shell at predetermined Zones along the outer shell for effecting a difference in temperature on a part of the outer shell of the temperature are arranged on the tiestlichen part of the outer shell. 13. · Device according to one of claims 10 to 12, characterized characterized in that the temperature control device comprises cooling means in the zone of the product end the outer shell is arranged. 14. Device according to one of claims 10 to 12, characterized characterized in that the temperature control device has a heater in the zone at the feed end the outer shell is arranged. - 114 - 409847/0701 15. Device according to one of claims 10 to 12, characterized characterized in that the temperature control device is heated in the central zone of the outer shell for heating the f'Uttelzone is arranged. 16. Device characterized by multiple sections Each of which is designed according to one of claims 10 to 12 is, by means of conduits, uch connect multiple sections with each other, by temperature- Control devices, uelche either with the multiple sections or the line means for maintenance connected by predetermined temperatures at the sections, 17. Device according to one of claims 10 to 12, characterized in that the polymeric material is one of of the group is uelche from perfluorosulfonic acid, dimethyl silicone, methyl vinyl silicone, fflethylphenyl silicone, Cellulose acetate, cellulose propionate, cellulose butyrate; from nylon IV, nylon VI and nylon VII, hydroxymethyl methacrylate, from copolymers of toluene diisocyanate, from polyester ^ such as polyurethanes, from polymers such as Polystyrene, polypropylene and / or. There is polyethylene, which is used to achieve hydrophilic properties Sulphonation, sulfur chlorination or by using comonamers, uie carboxylic acids and salts thereof is modified. A09847 / 0701 1B. Device according to one of Claims 10 to 12, characterized characterized in that the polymeric material is a solid perfluorocarbon polymer containing pendant groups composed of either of sulfonic acid or sulfonate or sulfonic acid and sulfonate. 19. The device according to claim 16, characterized in that each of the sections comprises a polymeric hollow member, the material of which is selected from the group consisting of made of perfluorosulfonic acid, dimethyl silicone, methyl vinyl silicone, Methylphenyl silicone, cellulose acetate, cellulose propionate, cellulose butyrate, nylon IV, nylon VI and Nylon VIII, hydroxymethyl methacrylate, from copolymers of tolaol diisodyanate, from polyesters such as polyurethanes, made of polymers such as polystyrene, polypropylene and / or eder There is polyethylene, which is used to achieve hydrophilic properties by sulfonation, sulfur chlorination or by using comonomers such as carboxylic acids and salts thereof is modified. 20, device according to claim 16, characterized in that each of the sections includes a polymeric hollow member made of solid perfluorocarbon polymer is that has subgroups of either sulfonic acid or sulfonate or sulfonic acid and sulfonate, - 116 - 409847/0701 21, a method for the selective separation of key components from a mixture of its components, characterized in that a supply line of components with one or more of the key components under a certain, initially relatively high pressure along and in contact with a layer of a permeable polymer membrane-like hollow member is guided, wherein the hollow member has a length as grcj 3ere 'Juerabmessung and the permeable polymeric membrane-like i ^v iaterial is selectively permeable to the key components in the feed stream?; that in countercurrent a second fluid stream essentially free of the key components separated under a lower pressure and with a composition different from the "feed stream" is guided by this through the wall of the polymeric permeable membrane-like hollow member; that the flow rates of the feed stream and the second fluid stream are so controlled that a concentration gradient along the entire length of the permeable polymeric hollow- member is maintained, thereby allowing the penetrable key components of the feed stream through the walls of the polymer 409847/0701 - ¹¹⁷ ~ Hollow members and in the second fluid flow through - or enter; and that the much less penetrative e Residue stream having selection components, as are present in the feed stream, is withdrawn. 22. The method according to claim 21, characterized in that the current volumetric flow rate of the second fluid stream is maintained at a Uert at least substantially equal to that is the current volumetric flow rate of the feed stream. 23. The method according to claim 21, characterized in that the ratio of the volumetric flow rates of the second fluid stream to the feed stream lies in a range between 1 and a value at which the residue flow is completely second Fluid flow is returned (total reflux). 24. The method according to claim 21, characterized in that either part or all of the residue flow is used as the second fluid stream. - 118 - 409847/0701 ~ 118 - 25. Continuous process for separating moisture of wet fluids, characterized in that a wet feed flow means through a or several of permeable membrane-like hollow members made of a perfluorosulfonic acid polymer are guided, the hollow members having a length greater than the transverse dimension and being permeable to water vapor that a second, relatively dry medium stream in countercurrent to the feed stream and therefrom separately through the permeable walls of the tubes uirdj that the flow rate of the second fluid stream is controlled so that the current volumetric Flow at least substantially equal to the value of the actual volumetric flow of the wet feed stream is, whereby water vapor is removed from the feed stream, so that sin water vapor pressure gradient and a water vapor concentration gradient across and maintained along the entire length of the walls of the tubes; and that the residue flow of the Feed stream is withdrawn as a substantially dry fluid, which is substantially less Has water vapor than is present in the wet feed stream. - 119 - 409847/0701 26. Uorfahren according to claim 25, characterized in that that the returned return flow is withdrawn and high-concentration components that have occurred therein be removed from it. 27. The method according to claim 26, characterized in that the returned RückfIui3strom in a Stripperst.ufe introduced uird, whereby the passage components arise in higher concentration, or that the residue stream of the feed stream is introduced into another permeation stage in order to achieve a to obtain poorer product in terms of the more permeable components. 20. The method according to claim 26, characterized in that that the feed component feed mixture is gaseous. 29. The method according to claim 26, characterized in that that the fluid is air. 30. The method according to claim 26 with self-clarification, characterized marked that the method is carried out in this way It becomes clear that P / F in the following equation is equal to odor is greater than 1: R PHi > -, P / F = ^x - 120 - uorin R is the reflux flow rate measured in standard volumetrics Units per unit of time, is based on the proportion of the total product flow rate, which is withdrawn from the system for external use, measured in the same standard units as R, uorin PHi denotes the full pressure in the high pressure phase at the product end of the system and in absolute terms Pressure units is measured, uorin PLo the pressure in the low pressure phase at the end of the system in which the reflux flows, denoted and measured in the same absolute pressure units as PHi, and where Ρ / Γ the ratio of the current volumetric flow of the reflux or clarification flow to the current volumetric flow of the feed flow and greater than 1 is. 31. Uorfahren according to claim 21, for use for the separation of carbon dioxide from fluids. 32. The method according to claim 21 for the application of Uasser and Carbon dioxide from hydrocarbon fluids. 33. l / experienced for drying fluids, characterized in that that a wet or moist feed stream under a predetermined pressure along and in contact - 121 - 409847/0701 with the hand of a single or a plurality of van per— meablen polymeric msrnbran-like hollow links are guided, the hollow links having a length greater than the quorum dimension and the polymeric permeable membrane-like material is selectively permeable to the feed stream present in the dome Water is daG a second stream, which is essentially free of the Uasser and from the feed stream through diaLJand dss polymeric permeable membrane-like hollow gliodes is separated, is guided in countercurrent; that the flow rates of both the feed stream and the second fluid stream are controlled so that a concentration gradient is maintained along the length of the permeable polymeric hollow member, whereby the uiasser is made possible by the ulünde of the passing through polymeric rlohlglisdes and entering the second fluid stream; that the fluid product, which has substantially less water than present in the feed stream, is withdrawn will; and that the temperature of the selected zones of the polymeric hollow member is controlled. 34. Uerfahren according to claim 33, characterized in that dai3 the product zone is cooled. 409847/0701 - 122 - 35. l / experience according to claim 33, characterized in that the SpoisBZonß is heated up. 36. I / experience according to claim 33, characterized in that the feed flow is kept at a partial temperature which is higher than that of the product zone and in the range between -17.2 and + 93 ° C (1 to 20 ° F) ₀ 37. Uerfahren according to claim 33, characterized in that the foodstuff is wet bezol. 38. Uerfahren according to claim 33, characterized in that the feed stream contains entrained or dissolved water. 39. Uerfahren according to claim 33, characterized in that the feed stream contains liquid water. 40. uerfahren according to claim 33, characterized in that the feed stream is preheated. 41. The method according to claim 33, characterized in that the second feed stream uorgekühlt uird before it is transferred to the Wall of the polymeric permeable membrane-like hollow member led along, - 123 - 409847/0701 42. The method according to claim 33, characterized in that the feed stream at the feeder is ^: heated, that the feed stream is progressively cooled to a lower temperature and that the feed stream is then cooled at the product end. 43. l / experience according to claim 33, characterized in that the sewage gas is a vaporized liquid product. 45 _{O A} method for drying fluids, characterized in that either a single hollow tube or a bundle of tubes is immersed in a wet fluid, wherein the tube or the tube bundle is made of a polymeric material which is selectively permeable to water, that a dry one The flow medium flow is guided through the pipes under sufficient pressure so that a flow is created which leaves the system before it comes into equilibrium with the water vapor in the system. 46. The method according to claim 45, characterized in that the dry flow of fluid to a sufficient level low pressure is kept, so that a low flow is present, which equilibrates with the water vapor of the system before it escapes. - 1 24 - 409847/07 0 1 47. ancestors according to claim 45, characterized in that, among other things, the dry-Z Ströniungsmittalstrom is haltsn overall pressurized ualcher in iJeraich van at 0.07 to 3.5 (0.1 DENL, - pain to 50 pounds POIG) is . 40 «Method according to claim 45, characterized in that dn; j the fluid is heated up before a dry fluid flow is passed through the pipe. 49. The method according to claim 45, characterized in that da3 the dry mean flow stream at one temperature in the range from its freezing point to its critical Temperature is maintained. 50. The method according to claim 45, characterized in that the polymors material is a material made of Group is selected that consists of polyethylene, polystyrene, Teflon, polysulfones, cellulose, ZBlluloseestorn and Parfluorocarbon polymers with Mebengrouppsn of either Sulfonic acid or sulfonate is " 51. The method according to claim 45, characterized in that the dry fluid is ambient air. 52. The method according to claim 45, characterized in that the dry fluid is a material selected from the group 409847/0 70 1 - 125 - BATH ORIGINAL is made from benzene, isopropanol, and sulfuric acid Ethylene glycol. 53o A method according to claim 45, characterized in that the dai3 Uasserkondensat dam of fluid flow away Uird and the fluid stream at the wet fluid Tram uorbeigeführt Uird ₀ 54. A method for drying fluids, characterized in that either a single hollow tube or a bundle of tubes is immersed in a wet fluid, that a dry fluid flow is conducted at a sufficient fluid flow rate that a flow is maintained, at which point the system exits, beuor it reaches the Gleichgeuicht with the water vapor in the system _o 409847/0701 Blank page