CN103237598A

CN103237598A - Method and device for chemical conversion by means of equilibrium reaction between reactants, and method for determining at least one parameter of such a chemical conversion

Info

Publication number: CN103237598A
Application number: CN2011800583480A
Authority: CN
Inventors: P·吉约; I·瓦斯孔塞罗
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2010-10-15
Filing date: 2011-10-13
Publication date: 2013-08-07
Also published as: FR2966057A1; WO2012049427A3; FR2966057B1; EP2627442A2; WO2012049427A2

Abstract

The invention relates to a chemical conversion method which can be used to controllably force the evolution of an equilibrium chemical reaction between reactants, particularly in a milli-fluidic system. According to the method, a single-phase liquid reaction flow stream containing the reactants is obtained and then segmented to form a two-phase gas-liquid flow stream, such as to extract a co-product of the reaction in the gas phase of the two-phase flow stream from the liquid phase from the two-phase flow stream. Subsequently, at least one fraction of the gas phase is separated from the two-phase flow stream by means of gas permeation of the co-product.

Description

The assay method of at least one parameter of the method and apparatus of balanced reaction chemical conversion and this class chemical conversion between reactant

Technical field

The present invention relates to be undertaken by the balanced reaction between reactant a kind of method and a kind of device of chemical conversion.The invention still further relates to a kind of assay method that at least one parameter of the chemical conversion undertaken by the balanced reaction between reactant is measured.

The present invention relates to milli fluid (millifluidique) field, namely relate to the operation to the fluid of millimeter grade even littler grade, in this case, this represents by term " microfluid " sometimes.Now, milli fluid and microfluid are acknowledged as can provide excellent tools for gathering the basic physics chemical data, because milli fluid and microfluid particularly allow to be improved with respect to traditional chemical vessel heat transfer, allow less reactant consumption, bigger enforcement flexibility, and for running system in distance and the harmony between the time of staying.

Background technology

Under this background, the present invention relates to the observation to the chemical reaction between liquid reactants more especially, and described chemical reaction reaches its chemical balance quite rapidly in the system of observing.In this case, be understandable that, the progress of chemical reaction can not be increased, this is because the product of reaction and accessory substance obtain with separately equilibrium quantity, and this has limited observation significantly, has particularly measured the possibility of the parameter relevant with the Chemical Kinetics of conversion.

Summary of the invention

The objective of the invention is to propose a kind of method and a kind of device, described method and apparatus allows, particularly in milli fluid flow system inside, and the progress of " promotion " chemical reaction of observing in a controlled manner.

For this reason, object of the present invention is a kind of method of carrying out chemical conversion by the balanced reaction between reactant, in described method:

– provides the liquid homogeneous reaction stream that contains reactant,

-then with described liquid homogeneous reaction flow point section forming gas-liquid two-phase flow so that from the accessory substance of the liquid phase abstraction reaction of described gas-liquid two-phase flow to the gas phase of described gas-liquid two-phase flow,

-then, by the gas infiltration of described accessory substance, from described gas-liquid two-phase flow, separate at least a portion of its gas phase.

One of basic concept of the present invention is, in the controlled elimination of flowing reactive internal system enforcement to the described accessory substance of chemical reaction.Therefore, according to the present invention, after forming liquid homogeneous reaction stream, one after the other implement two lock out operation: first lock out operation is by the segmentation gas-liquid flow that utilizes liquid single-phase flow to obtain accessory substance to be carried out solution-air to extract, and second lock out operation is by the gas infiltration of this accessory substance at least, during milking the gas with producing that injects is carried out solution-air and separates.More definitely, it is relevant with the relative volatility in the liquid phase in the gas phase of two phase flow with accessory substance that first solution-air is extracted operation: there is the local evaporation that causes the accessory substance that exists in the liquid phase in the gas phase in the described stream, chemical balance is outer to be carried out with being reflected at forward so that so chemical system is in, come accessory substance loss is compensated, reach vapor-liquid equilibrium and chemical balance up to simultaneously.Gas phase then is full of accessory substance, be further " reinforcement " chemical conversion process, two phases that the permission of second lock out operation separates described stream at least in part even fully: for this reason, at least one gas part that contains accessory substance of two phase flow is eliminated from two phase flow by the gas infiltration, this so that in check mode chemical reaction is advanced.In fact, aforesaid solution-air is extracted then solution-air and is separated this two kinds of operations, and the repetition that advantageously circulates is with the extent of reaction eliminating accessory substance more and more and allow to reach higher and thereby reach increasing product weight.

In fact, the method according to this invention advantageously can be implemented under higher running temperature and pressure, and typically running temperature and pressure are respectively greater than 100 ℃ with greater than 30 bar.Therefore be appreciated that the benefit that the method according to this invention is applied to polymerisation, particularly polycondensation reaction.Just in this background, the inventor has given prominence to the favourable supplementary features of some in addition, and these features will be described hereinafter in more detail.

The favourable additional aspect of the method according to this invention---they adopt individually or according to technical possible various combinations:

-after forming described gas-liquid two-phase flow, from described gas-liquid two-phase flow, by the whole gas phase of gas permeability and separation, make it stand one or more additional segmentations and separating cycle then;

-be at least a portion of from described gas-liquid two-phase flow, separating its gas phase, use gas-permeable membrane, the permeability to accessory substance that described gas-permeable membrane has is higher than the permeability to other composition of described gas phase, preferably to the twice at least of the permeability of other composition of described gas phase;

-using organic permeable membrane, described organic permeable membrane is particularly based on polymeric material;

-using inorganic permeable membrane, described inorganic permeable membrane is particularly based on pottery and/or zeolite;

-be with described liquid homogeneous reaction flow point section, inject gas for reactionlessness between reactant in stream mode altogether therein;

-the gas flow that injects be selected as described gas-liquid two-phase flow total volumetric flow rate 5% to 95% between;

-the flow of described liquid homogeneous reaction stream at 0.01mL/h between the 1000mL/h, preferably at 1mL/h between the 50mL/h;

-chemical conversion reaction is polymerisation, particularly polycondensation reaction.

Object of the present invention also is the assay method at least one parameter of the chemical conversion of being undertaken by the balanced reaction between reactant, in described assay method:

-according to as above define described method carry out chemical conversion and

-gas-liquid two-phase flow that separates at least a portion of its gas phase from gas-liquid two-phase flow is measured, described at least one parameter to infer thus.

Object of the present invention is a kind of device that carries out chemical conversion by the balanced reaction between reactant in addition, and described device comprises:

-solution-air segmentation module, its liquid single-phase flow that is suitable for containing reactant is segmented into gas-liquid two-phase flow so that from the liquid phase of described gas-liquid two-phase flow the accessory substance of abstraction reaction in the gas phase of described gas-liquid two-phase flow and

-solution-air separation module, the import of described solution-air separation module links to each other with the outlet of described solution-air segmentation module, and described solution-air separation module is suitable for the gas infiltration by accessory substance, separates at least a portion of its gas phase from described gas-liquid two-phase flow.

According to a preferred embodiment, described solution-air separation module comprises gas-permeable membrane, and described gas-permeable membrane is arranged in the circulating line of gas-liquid two-phase flow in supported mode and from the gas phase of described gas-liquid two-phase flow and pass between the dispatch pipeline of gas of described gas-permeable membrane.

Description of drawings

By reading the ensuing explanation that only provides as example and carry out with reference to accompanying drawing, the present invention will be better understood, in the accompanying drawing:

-Fig. 1 is the schematic diagram according to the facilities and equipments of chemical conversion process of the present invention;

-Fig. 2 is the schematic cross sectional views along the line II-II of Fig. 1; With

-Fig. 3 is the view similar to Fig. 2, illustrates according to of the present invention one and implements modification.

The specific embodiment

The equipment of Fig. 1 at first comprises upstream line 10, and described upstream line is supplied with by liquid homogeneous reaction mixture.Flow in pipeline 10 is advantageously between 0.01 to 1000mL/h, preferably between 1 to 50mL/h.Therefore, by this range of flow, the equipment of Fig. 1 can be called as the milli fluid device, even microfluidic device, and pipeline 10 typically realizes that with form capillaceous for example make with stainless steel, its diameter is about 1 millimeter.

The liquid reaction stream of implementing in pipeline 10 obtains by two or more liquid reactant of combined upstream at pipeline 10, and this is undertaken by any suitable components, will not carry out more deep description for these parts here.

In the reaction stream of in pipeline 10, implementing, between at least two kinds of reactant R1 and R2, produce the equilibrium chemistry reaction, obtain at least a product P and at least a accessory substance C.As the example of being carried out the object of multiple operation by the invention people, reactant R1 and R2 are adipic acid and ethylene glycol, these compositions react according to polyesterification reaction, forming polyethylene glycol adipate (polyadipate d' é thylene) as product P, and with moisture as accessory substance C.In other words, aforementioned exemplary is polycondensation reaction, and it provides polyethylene glycol adipate according to the predetermined ratio separately relevant with the equilibrium property of the polycondensation chemical reaction that takes place with the upstream in pipeline 10, and forms moisture.

In fact, the liquid homogeneous reaction stream of implementing along pipeline 10 advantageously carries out under gratifying temperature and pressure condition, to realize the chemical reaction of expectation.For this reason, pipeline 10 and allow mixed reactant R1 and therefore the parts of R2 are designed it should be explicitly made clear at this point, in corresponding layout belongs to those skilled in the art's the scope of Tool Knowledge, will not carry out more deep description to these corresponding layouts here.Mentioned above and the scope of polycondensation example in, the reaction stream in pipeline 10 is with about 200 ℃ and obtain under the pressure of 50 bar.

Because the equilibrium property of the chemical reaction that produces in pipeline 10, thereby the progress of this reaction must be restricted, and this is because after the certain time of staying in pipeline 10, react and reach its chemical balance, product P and the accessory substance C of acquisition predetermined quantity.

According to the present invention, the lower exit of pipeline 10 is supplied with solution-air segmentation module 20.As schematically represented on Fig. 1, this module 20 comprises T shape element 21, and main split's part of T shape element is connected with pipeline 10, and its transverse branch partly is furnished with gas injection capillary 22, and this capillary is supplied with by source of the gas 23.Therefore, transverse branch downstream partly at T shape element 21, module 20 comprises pipeline 24, flows altogether this pipeline 24 from the liquid reaction mixture of pipeline 10 and the gaseous flow that flows out from capillary 22 stream, and capillary 22 and pipeline 24 extend in mode coaxially to each other.As for pipeline 10, pipeline 24 is for example implemented with the form capillaceous of about 1 mm dia, stainless steel.In pipeline 24, the gas that is injected by capillary 22 produces bubble, and these bubbles are separated by twos by liquid volume.In other words, module 20 can be segmented into gas-liquid two-phase flow with the liquid single-phase flow from pipeline 10.Instrument in module 20 is arranged as in the scope well known to those skilled in the art, and here no longer more in depth the instrument of describing module 20 is arranged.The reader can be particularly with reference to " The Role of Gas Bubbles and Liquid Slug Lengths on Mass Transfer in the Taylor Flow throught Taylor Capillaries(stream is by the effect to mass transfer of bubble in the capillary and fluid block length) " (Chem.Eng.Sci.1997 of existing document G.Bercic and A.Pinrat, 52,3709), and T.C.Thulasidas, M.A.Abraham and R.L.Cerro " the bubble train stream in Bubble-Train Flow in Capillaries of Circular and Square Cross-Section(circle and the square cross section capillary) " (Chem.Eng.Sci.1995,50,183).

In fact, for the important operating parameter of two phase flow in the pipeline 24 that obtains to be segmented in good mode uniformly, relevant with the gas flow that injects by capillary 22.Advantageously, the volume fraction of institute's injecting gas, namely the ratio of the gas flow of Zhu Ruing and the total volumetric flow rate of pipeline 24 is selected between 5% to 95%.If it is bigger that the volume fraction of gas is selected as, then may take place in the meaning of wall " crawling (the rampant) " phenomenon along pipeline 24 at described stream, the systematicness of the segmentation of gas-liquid two-phase flow may suffer damage, and this can produce the control problem of the time of staying in equipment.On the contrary, for the reason of stating hereinafter, still expect the gas volume branch rate of bigger numerical.

Gas in the flow in pipes 24 is used for causing that accessory substance C that the liquid phase that is extracted in this stream exists is in the gas phase of the described stream of pipeline 24.The power of this extraction is the relative volatility of accessory substance C in aforesaid gas phase and liquid phase.In fact, thereby be understandable that employed gas is for reactant R1 and R2, product P and accessory substance C inert gasses.This typically relates to neutral gas.In the example of the polycondensation reaction that reaches mentioned above, this gas for example is argon: the existence of Argon Bubble causes the part evaporation of the moisture that exists in the liquid phase of the described stream of pipeline 24, as indicated by the arrow 25 on Fig. 1.So the chemical system of the liquid phase of the described stream of pipeline 24 is in outside the chemical balance, being reflected on the forward (sens direct) between reactant R1 and the R2 carried out, with the moisture loss of compensation in liquid phase, up to the chemical balance and the vapor-liquid equilibrium that reach simultaneously in liquid phase.Gas phase then is full of water.

Certainly, be understandable that the temperature and pressure operating condition that exists at pipeline 10 places should be held in segmentation module 20, with the progress of the reaction between lifting reactant R1 and the R2, and not disturbed by the temperature and pressure condition.

Also according to the present invention, the outlet of pipeline 24 be connected with visible solution-air separation module 30 on Fig. 2 at Fig. 1.In the illustrative examples of considering on these accompanying drawings, module 30 comprises two

main bodys

31 and 32, and in use, these of two main bodys mechanically assemble on another.Main body 31 in the surface of main body 32, is had pipeline 33 at it, and the end, upstream of pipeline 33 is connected with the outlet of pipeline 24.Main body 32 in the surface of main body 31, is then had pipeline 34 at it, and pipeline 34 is faced mutually with pipeline 33 and arranged.Pipeline 33 and 34 is similar to the milli fluid and leads, and similar with 24 to pipeline 10, having full-size is about 1 millimeter cross section.These

pipelines

33 and 34 are spaced from each other by gas-permeable membrane 35 and the supporter 36 that is used for this gas-permeable membrane simultaneously.Gas-permeable membrane 35 and supporter 36 nestle layout mutually, and planting also, machinery remains between

main body

31 and 32.

Gas-permeable membrane 35 is implemented with such material, compares with the inert gas of source of the gas 23, and this material can be beneficial to accessory substance C and pass this film infiltration.In fact, this comes from such fact: constitute the permeability for accessory substance C that the material of gas-permeable membrane 35 has, the permeability of gas that is compared to source of the gas 23 is higher, preferably for the twice at least of the permeability of the gas of source of the gas 23.36 of supporters are by porous material, typically porous metals constitute, and pass gas-permeable membrane 35 and freely circulate up to jointed pipe 34 through the gas componant of its infiltration.Thereby be understandable that supporter 36 has so main even single-minded function: machinery keeps gas-permeable membrane 35, in particular for the permeable membrane part that is arranged between pipeline 33 and 34.In other words, under the situation that does not have supporter 36, gas-permeable membrane 35 has the risk that irreversible damage takes place under the pipeline 34 sides effect of upwarding pressure for stream in pipeline 33.

Advantageously, permeable membrane 35 is so-called dense film, and namely its separation principle is based on the permeable membrane on sorption and the flooding mechanism in the selection layer of this permeable membrane.This class dense film has such advantage: can use under high operating pressure, operating pressure is typically greater than 30 bar, even greater than 50 bar, as this be for mentioned above and the situation of example of polycondensation reaction.Especially, the inventor pays close attention to the fine and close permeable membrane of particularly making based on the organic material of polymeric material 35.Therefore, mentioned above and the scope of example of polycondensation reaction in, the inventor is DUPONT(Du Pont) company is registration mark with reference number TEFLON-AF-2400(word " TEFLON(Te Fulong) ") material of putting on market is as the preferred material for the manufacture of permeable membrane 35.This material since its to the high permeability of low-molecular-weight gas, particularly to the high permeability of steam, and selected.

As modification, fine and close permeable membrane 35 can be with particularly with pottery, and zeolite etc. are made for the inorganic material on basis.

Still under the background of the temperature and pressure operating condition that reaches mentioned above, can point out that as example, the

main body

31 and 32 of module 30 is made with stainless steel, these main bodys fitted together along a plurality of screws that distribute mutually by the week along these main bodys.36 of supporters are for example implemented with the form of stephanoporate steel plate.

In use, along with the two phase flow from pipeline 24 flows along pipeline 33, the accessory substance C that contains in the gas phase of this stream enters in the permeable membrane 35, up to passing permeable membrane and porous supporting body 36, thereby enter pipeline 34, as pointed by arrow 37 at Fig. 1 and Fig. 2.Be understandable that, by permeable membrane 35 selective for accessory substance C, compare with other gas with from source of the gas 23 that exists in the gas phase of two phase flow, the effect of permeable membrane 35 allows to separate from two phase flow at least a portion of its gas phase, makes its gas phase exhaust existing accessory substance C.In other words, by the permselective property for accessory substance, avoid making gas phase supersaturation aspect accessory substance of described two phase flow, this can cause this accessory substance to the liquid phase condensate of described stream.Mentioned above and the situation of example of polycondensation reaction in, this says in fact, in separation module 30 inside, the moisture of the gas phase of two phase flow is permeated quickly than argon, this causes that steam exhausts in the bubble, thereby cause that moisture is from the liquid phase evaporation of described stream, so that the gas of bubble recovers aspect steam.

Therefore permeable membrane 35 causes the extra evaporation of moisture, causes the extra evaporation of accessory substance C more in general manner, and this obviously is conducive to forward reaction, thereby is conducive to obtain the bigger progress of this reaction.Certainly, permeable membrane 35 is selected to the gas phase that only allows two phase flow and passes this film, and whole liquid phase still remains in the pipeline 33.

In fact, by giving solution-air separation module 30 suitable definite sizes, the whole gas phase that in the two phase flow from pipeline 24, exists advantageously from this flow point from, this says with ining fact, exports at pipeline 33, the stream of discharging is liquid single-phase flow.

The gas that has arrived pipeline 34 is discharged from this pipeline by this pipe downstream end, as pointed by the arrow 38 on Fig. 1.Advantageously, stagnate in pipeline 34 for avoiding these gases, the end, upstream of this pipeline can be supplied with gas superpressure slightly, causes the cleaning effect with the direction towards its downstream end in pipeline 34, as pointed by arrow 39.

Pipeline 10, solution-air segmentation module 20 and solution-air separation module 30 thereby formation milli fluid means can be called this milli fluid means the milli reactor, and it can control the movement that reaction arrives the progress of molecular balance.

The outlet of pipeline 33 then is connected with the downstream line 40 of equipment, and the downstream line of equipment is passed measuring unit 50 as shown on Fig. 1.By suitable arrangement, this measuring unit 50 allows the stream of circulation in pipeline 40 is measured, as measures its viscosity or component.As example, particularly mentioned above and the scope of example of polycondensation reaction in, this measuring unit 50 is HPLC unit, and it is acronym HPLC(High Performance Liquid Chromatography HPLC in English often) represent.In fact, independently or the multiple measurement component that replenishes can be integrated in 50 inside, unit, carry out the measurement type of desired most amounts with the stream to pipeline 40.

On the basis of the measurement result of being undertaken by unit 50, infer with reactant R1 and R2 between one or more parameters of the relevant chemical conversion of reaction, the parameter relevant with the Chemical Kinetics of this conversion particularly, as extent of reaction, with and speed and its activation energy.

In the scope of the literature, do not further describe with unit 50 relevant and relevant with the utilization of the measurement of being undertaken by this unit technology and consider, because they are in those skilled in the art's limit of power, what need simultaneously to draw attention to is, these technology are considered and can be taked very various form, and the present invention are not formed restriction.

As selection, the equipment of Fig. 1 also comprises return line 60, and it is only shown in broken lines on Fig. 1.This return line 60 is set up in order to whole streams or the part stream that will circulate in downstream line 40 and sends back in upstream line 10.Like this, equipment can make liquid homogeneous reaction mixture respectively by solution-air segmentation module 20 and solution-air separation module 30, stands a plurality of segmentation and separating cycle in succession.

In addition, multiple layout and the multiple modification of the equipment of Fig. 1 and its implementation method can be considered.

Therefore, as example, solution-air separation module 30 can be implemented with the form of the modification 30 ' shown on Fig. 3: for sealing purpose, packing ring 30 ' .1 and 30 ' .2 are attached between main body 31 ' and the permeable membrane 35 ' respectively and are used between the supporter 36 ' and main body 32 ' of permeable membrane 35 ', wherein, main body 31 ' is similar to the main body 31 of module 30 on function, permeable membrane 35 ' is similar to the permeable membrane 35 of module 30 on function, supporter 36 ' is similar to the supporter 36 of module 30 on function, and main body 32 ' is similar to the main body 32 of module 30 on function.As example, packing ring 30 ' .1 and 30 ' .2 make with the epoxidation resin.Advantageously, implement in the modification at this, the circulating line 33 ' of two phase flow defines by packing ring 30 ' .1 at least in part.Similarly, the dispatch pipeline 34 ' that has passed the gas of permeable membrane 35 ' partly defines by packing ring 30 ' .2.

Similarly, as the modification that does not show for solution-air separation module 30 and 30 ', the circulating line 33 or 33 ' of gas-liquid two-phase flow is not limited to single component, but on the contrary, can be made up of a plurality of the leading of dendriform or multi-branched, its end, upstream and downstream end with pipeline 33 or 33 ' couples together each other.Dispatch pipeline 34 or 34 ' for gas is like this equally.

Claims

1. carry out the method for chemical conversion by the balanced reaction between reactant, in described method:

-provide contain reactant (R1, liquid homogeneous reaction stream R2),

-then with described liquid homogeneous reaction flow point section forming gas-liquid two-phase flow so that from the accessory substance (C) of the liquid phase abstraction reaction of described gas-liquid two-phase flow to the gas phase of described gas-liquid two-phase flow,

-then, by the gas infiltration of described accessory substance (C), from described gas-liquid two-phase flow, separate at least a portion of its gas phase.

2. method according to claim 1 is characterized in that, after forming described gas-liquid two-phase flow, separates whole gas phase by the gas infiltration from described gas-liquid two-phase flow, makes it stand one or more additional segmentations and separating cycle then.

3. method according to claim 1 and 2 is characterized in that, for separate at least a portion of its gas phase from described gas-liquid two-phase flow, uses gas-permeable membrane (35; 35 '), the permeability to accessory substance (C) that described gas-permeable membrane has is higher than the permeability to other composition of described gas phase, preferably to the twice at least of the permeability of other composition of described gas phase.

4. method according to claim 3 is characterized in that, uses organic permeable membrane (35; 35 '), described organic permeable membrane is particularly based on polymeric material.

5. method according to claim 3 is characterized in that, uses inorganic permeable membrane, and described inorganic permeable membrane is particularly based on pottery and/or zeolite.

6. according to each described method in the aforementioned claim, it is characterized in that, for described liquid homogeneous reaction flow point section, inject therein in the mode that flows altogether that (R1, R2) reaction between is inert gasses for described reactant.

7. method according to claim 6 is characterized in that, the gas flow that injects be selected as described gas-liquid two-phase flow total volumetric flow rate 5% to 95% between.

8. according to each described method in the aforementioned claim, it is characterized in that, the flow of described liquid homogeneous reaction stream at 0.01mL/h between the 1000mL/h, preferably at 1mL/h between the 50mL/h.

9. according to each described method in the aforementioned claim, it is characterized in that the chemical conversion reaction is polymerisation, particularly polycondensation reaction.

10. to the assay method of at least one parameter of the chemical conversion undertaken by the balanced reaction between reactant, in described assay method:

-according to each described method in the aforementioned claim carry out chemical conversion and

-gas-liquid two-phase flow that separates at least a portion of its gas phase from gas-liquid two-phase flow is measured, to infer described at least one parameter thus.

11. by the device that chemical conversion is carried out in the balanced reaction between reactant, described device comprises:

-solution-air segmentation module (20), its be suitable for contain reactant (R1, liquid single-phase flow R2) is segmented into gas-liquid two-phase flow so that from the liquid phase of described gas-liquid two-phase flow the accessory substance of abstraction reaction (C) in the gas phase of described gas-liquid two-phase flow and

-solution-air separation module (30; 30 '), the import of described solution-air separation module links to each other with the outlet of described solution-air segmentation module (20), and described solution-air separation module is suitable for the gas infiltration by accessory substance (C), separates at least a portion of its gas phase from described gas-liquid two-phase flow.

12. device according to claim 11 is characterized in that, described solution-air separation module (30; 30 ') comprise gas-permeable membrane (35; 35 '), described gas-permeable membrane is arranged in the circulating line (33 of gas-liquid two-phase flow in supported mode; 33 ') with from the gas phase of described gas-liquid two-phase flow and pass the dispatch pipeline (34 of the gas of described gas-permeable membrane; 34 ') between.