CN1060040A - The liquid-film method of divided gas flow - Google Patents
The liquid-film method of divided gas flow Download PDFInfo
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- CN1060040A CN1060040A CN 90107832 CN90107832A CN1060040A CN 1060040 A CN1060040 A CN 1060040A CN 90107832 CN90107832 CN 90107832 CN 90107832 A CN90107832 A CN 90107832A CN 1060040 A CN1060040 A CN 1060040A
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Abstract
A kind of being used for is permeating airflow that mainly has low balance K value and the liquid-film method that mainly has the gas flow of higher balance K value with flow separation, wherein, input air-flow and liquid film are operated under the temperature and pressure of the input air-flow dew point in the liquid/gas two phase region that approaches phase boundary, thereby in the input air-flow, produce cohesion, for liquid film provides liquid.Liquid-film method is for separating hydrocarbon gas, and the natural gas that comprises high-load methane as separation is imported air-flow, is useful especially.
Description
The present invention is the method for divided gas flow, is specifically related to the liquid-film method of divided gas flow.
The flow process costs of handling natural gas and the various gathering oil of recovery are used in gas with major part and separate.At first, the ethane in the natural gas, propane and higher alkane thing must be removed, to obtain salable methane product.And then higher alkane material is used for multiple purpose.For further separating higher alkane material, may also need other separation.
The various recovery process costs of assembling oil also are used in gas with major part and separate.Use carbon dioxide or middle hydrocarbon to make miscible impregnating agent and usually require the intermixture that separates and reinject and produce, it is economical doing like this.
Most of cost of handling gas is separated from the gas relevant.Cryogenic separation need spend big compression and refrigeration operation.Absorb the solvent recovery of processing requirements costliness.For avoiding the big operation of most of power consumption and reducing investment and running expense, just carrying out the research of thin film technique now.
Polymer film is used in a lot of technologies, and foremost is the Prism method of Meng Shandou (Monsanto), and the shortcoming of polymer film is that the flow by film on unit are is very little.This just means that the surface area of system must be very big.The Prism method has been used the narrow tube of the bunchy of end obstruction in the structure of heat exchanger.This has just strengthened the surface area of separator, but in order to reach suitable flow rate, it is sizable that device remains.
Because liquid film has higher permeability, so liquid film can reach bigger flow on unit are.The second, the separation of liquid film also may be higher than polymer film.The 3rd, the shortcoming of polymer film is, it preferentially carries low-molecular-weight material, and for a lot of separating technologies, this low-molecular-weight material has constituted the major part of gas volume.Different with it, the preferential gas of carrying of liquid film, and for separation with low balance K value, separation of alkane material for example, these gases are the less and heavier alkane of volume.
The most familiar liquid film is the aqueous solution of making activating agent with the carrier complex compound.In a kind of like this technology, compound has experienced reversible reaction in the upstream and downstream both sides of liquid film.It is inappropriate that this film is used for transportation of hydrocarbon, but is used for sour gas and carbon dioxide or hydrogen sulfide, and then performance is fine.
At M.S.Brennan, A.G.Fane and C.J.D.Fell are entitled as " the liquid film separating natural gas that utilization is supported " (AIChE Journal, Vol.32, NO.1, P.558(1986)) in the paper, with be entitled as " utilizing the hydrocarbon liquid film to separate the experiment of hydrocarbon gas " (American Institute of Chemical Engineers (AIChE) at John K.Dobitz, autumn session, November 15～18 in 1987, New York) disclosing in the paper utilizes the hydrocarbon liquid film to come the hydrocarbon gas of separate low molecular amount.
The present invention is a kind of liquid-film method, be used for becoming infiltration gas based on gas to flow the flow separation and flow based on the gas of gas with higher balance K value with low balance K value, this method comprises: gas input air-flow is contacted with the liquid film that is supported, discharge the air-flow based on gas that can not penetrate liquid film from the upstream side of liquid film, and discharge to have the air-flow that penetrates liquid film than the gas that hangs down balance K value from the downstream of liquid film with higher balance K value.
Input air-flow and liquid film are operated under the temperature and pressure of the input air-flow dew point in the liquid/gas two phase region that quite approaches phase boundary, make to import condensation, for liquid film provides liquid.Liquid-film method for example separates the natural gas input air-flow that comprises a large amount of methane for separating hydrocarbon gas, is useful especially.
The present invention relates to the liquid film of divided gas flow, wherein, the temperature and pressure of supplying with the input air-flow of liquid film is controlled to the dew point that quite approaches to import air-flow, makes in the input air-flow condensation takes place, for liquid film provides liquid.When the component of input air-flow changes, then adjust the operating temperature and the pressure of input air-flow and liquid film, to keep supplying with the needed condensation number of liquid film.This method has solved the subject matter that liquid is provided again in liquid membrane separating method.
The hydrocarbon liquid film that is supported has particularly proved in the separation of hydrocarbon gas and has got a good chance of in the gas that is difficult to carry out separates.In this liquid film, effective as selective is controlled by vapour-liquid equilibrium.Mass transport is realized by diffusion.Promoting the required concentration gradient of diffusion is provided by two the lip-deep vapour-liquid equilibriums of upstream and downstream at liquid film.Therefore, separate component, operating temperature and the pressure that depends on input and permeating airflow.
Main difference between vapour-liquid equilibrium film and other film is the component that the composition that passes film can significantly change film liquid.The change of this component will change the vapour-liquid equilibrium that the gas with the liquid film contact both sides reaches, and change total separation of liquid film system when the composition of input penetrates liquid film.
Main conveying mechanism by liquid film is considered to Fick (Fiokian) diffusion.Concentration gradient is set up by vapour-liquid equilibrium in both sides at liquid film.Concentration is under pressure, the influence of the component of temperature, the gas component that contacts with liquid film and liquid film itself.Think also that simultaneously the body air-flow in liquid film is negligible.Because the vapour-liquid equilibrium of liquid is non-linear for pressure, so must use the concentration gradient model.
According to top hypothesis, mole (gram molecule) flux of the i composition by liquid film is:
Qi＝ (ADi)/(t) （Ci
1-Ci
2）
In the formula, Qi is the molar flux (mol/s) of component i; A is the area (m on liquid film surface
2); Di is the diffusion coefficient (mol/s/m/mol%) of component i in the enriching apparatus relevant with the support liquid system; Ci
1It is the strength of fluid of the component i of input side; Ci
2It is the strength of fluid of the component i of per-meate side; T is the thickness (m) with liquid film of support.
The concentration of surface composition such as Ci in the liquid film body
1And Ci
2Can utilize balance K value to calculate, wherein,
Ki＝yi/Xi
Xi is the strength of fluid of component i in the formula; Yi is the vapour concentration of component i.
Liquid film will preferentially be carried the gas with low balance K value.Therefore for the natural gas of being made up of alkane, the alkane great majority of the higher molecular weight that propane is above will penetrate the hydrocarbon liquid film, and methane and a large amount of ethane can not pass liquid film.Yet between higher balance K value and lower molecular weight, there is not direct dependency relation.For example under the pressure of 100 temperature and 100 pounds/square inch, the balance K value of ethene is 0.7, and the balance K value of ethane is 6.0.Although therefore the molecular weight of ethene is less, ethene will penetrate the hydrocarbon liquid film very soon, and ethane will be stayed the upstream side of liquid film.
Comprise and have not that the air-flow of homostasis K value composition utilizes the present invention effectively to separate.The separation that can be difficult to, the separating of for example above-mentioned ethene and ethane.The separation that another that is suitable for carrying out with the present invention is difficult to is separating of butane and iso-butane.These two kinds of alkane have different balance K values, although they have identical molecular weight.Utilize liquid film of the present invention can also separate ammonia, separation of methane and the hydrogen in other gas such as nitrogen and the hydrogen and separate halogen gas.
For the requirement that improves operating temperature with some are separated easily carry out, can be in the input air-flow a kind of compound of adding, the amount of its adding should be enough to make the compound of adding to provide agglomeration liquid for liquid film.For example in the separating of methane and hydrogen, should add have four carbon atom at least hydrocarbon in the input air-flow so that supply with liquid film.A shortcoming of doing like this is must remove the hydrocarbon of adding afterwards from the product air-flow.Add the hydrocarbon have four carbon atom at least in the input air-flow, the hydrocarbon that the amount of its adding should be enough to make adding is for liquid film provides the liquid of cohesion, adopts this method can more effectively carry out as an example ethane and the separating of ethene.
Input air-flow and liquid film should remain under the temperature and pressure of the input air-flow dew point in the liquid/gas two phase region that quite approaches phase boundary, so that the compound that adds cohesion from the input air-flow comes out, thereby provide liquid for liquid film.The compound of some addings will pass liquid film, and some upstream sides at liquid film evaporate.The compound that therefore must add q.s in the input air-flow so that replenish the loss of the compound that is added on the liquid film, and keeps liquid film perfect, is two kinds of required air-flows thereby will import flow separation.
It is useful especially that liquid-film method separates for natural gas, wherein, methane is separated from heavier alkane.Most of natural gases mainly are methane, also contain some ethane and heavier alkane.When method begins, natural gas input air-flow is contacted with hydrocarbon liquid film on support, natural gas is imported air-flow mainly by the gas composition of molecular weight less than decane.By being soaked into, support have at least the hydrocarbon liquid of six carbon atom to form liquid film.One when liquid film formation, depends on operating temperature and pressure, and the alkane that overweights ethane just produces cohesion, and this cohesion will provide liquid for liquid film.
Main methane gas can not pass liquid film, can discharge from the upstream side of liquid film.Permeating airflow by the gas composition that has two carbon atoms at least can be discharged from the downstream of liquid film.A spot of methane can pass liquid film.Make permeating airflow once more or manyly pass other liquid film several times.Just can remove this undesirable methane.Using the liquid film system to carry out one or many with the same manner separates, also can make the heavier alkane separation of permeating airflow become two or more air-flows.
Natural gas input air-flow also may comprise nitrogen, hydrogen sulfide, carbon dioxide, helium or water.These compounds mainly are trapped in the upstream side of liquid film, can not pass the hydrocarbon liquid film in large quantities.
When partition method begins, in case liquid film can carry out just producing for liquid film provides same a kind of compound of agglomeration liquid or identical several compounds with partition method.Also possible, and also wish in some cases to utilize the compound that does not have in the input air-flow to produce liquid film.But under any circumstance, one or more compositions that provide agglomeration liquid for liquid film in the input air-flow are at the initial formation material that will finally replace liquid film after after a while.
Concerning the natural gas separating technology, preferably use the more stable difficult compound that volatilizees to form the liquid film of beginning, this compound will guarantee that liquid film can last till that processing technology reaches stable state.The initial formation material of liquid film such as crude oil are a kind of materials of and difficult volatilization more stable than butane, pentane and hexane, and after the natural gas separating technology reaches stable state, butane, pentane and hexane perhaps will become the main component of liquid film.
Making support soak into selected liquid is in order to form liquid film fully.Certainly, many liquid compounds can be used for forming the liquid film of beginning, as long as liquid film can last till that technology reaches stable state and the input air-flow can provide sufficient coagulation liquid to keep and additional liquid film.For the separation of hydrocarbon, the most handy heavier nonvolatile hydrocarbon produces the liquid film of beginning.Because there are ten or still less the alkane of carbon atom and kerosene evaporation are very fast approximately, so it is good not as the initial formation material of making liquid film with oily type paraffin wax or resinite hydrocarbon, carbenes hydrogen compound, alkane or other nonvolatile hydrocarbon to make the initial formation material of liquid film with them.For the separation of hydrocarbon, the most handy hydrocarbon liquid of selecting from such one group of material is soaked into support, produces the liquid film of beginning, and this group material comprises kerosene, has the alkane of ten carbon atoms at least, vaseline, oily type paraffin wax and C
7+The crude oil that content is high.
In order to help to make liquid film keep its globality, need the support of some pattern.For supporting liquid film, some filter support is good structure.Though preferably support can be different according to separating technology, in general preferably use the support of screen size less than about 5000 dusts.In some cases, screen size is less than possible best of the support of about 50 dusts.Less hole dimension generally will provide stronger and more stable liquid film.The liquid film of less screen size can bear higher pressure differential, because it has the higher point pressure that steams.
Also may wish to use purge gas in some cases, so that help to discharge the permeating airflow of gas from the downstream of liquid film.Can application examples in stratochamber separates such as helium make purge gas, but perhaps do not wish use this gas, because purge gas must be separated from the product air-flow that permeates industrial.In large-scale the application, increasing pressure reduction just can be without purge gas.
Following Example can further specify the liquid film of novelty of the present invention.These examples only are used for explanation, do not constitute the restriction to invention scope.Therefore should be understood that,, can change the composition of processing step and liquid film in order to reach similar results within the scope of the present invention.
Experimental data proves that oil gas can separate with the hydrocarbon liquid film.These experiments are carried out on stainless micropore 90mm filter seat.What replace this filter is GVHP microporous polymer (polyvinylidene fluoride) filter that is used as support.The size of this filter sieve mesh is about 2000 dusts.This support soaks into kerosene and is placed on the filter seat.The input air-flow is made of the low hydrocarbon-enriched flow air-flow that gas/the oil ratio production fields obtains of simulation.The component of input gas is listed in table 1.
Table 1
Methane 30.07%
Ethane 27.86%
Propane 12.81%
Iso-butane 1.23%
Normal butane 4.06%
Isopentane 0.84%
Pentane 1.38%
Hexane 0.91%
Nitrogen 2.93%
Carbon dioxide 17.88%
At upstream pressure is 35 pounds/square inch and the downstream of liquid film when using helium purge, has measured the concentration in downstream.Separate and carried out 13 times.Numeral in table 2 and the table 3 has been indicated the mean value of 13 operations.
Table 2
Methane 0.67%
Ethane 2.21%
Propane 1.93%
Iso-butane 0.24%
Normal butane 1.01%
Isopentane 0.27%
Pentane 0.49%
Hexane 0.43%
Nitrogen 0.06%
Carbon dioxide 0.95%
Helium equilibrium valve %
Can obtain the separation of table 3 by top data.
Table 3
Methane 1.000
Ethane 3.89
Propane 8.22
Iso-butane 11.39
Normal butane 16.02
Isopentane 23.85
Pentane 28.74
Hexane 53.74
Nitrogen 1.00
Carbon dioxide 2.52
All separations are all with respect to methane.In other words, the separation of ethane is 3.89, and its expression ethane passes liquid film and passes easy 3.89 times of liquid film than methane.Be separated under room temperature and the low pressure condition and carry out.A kind of like this liquid-film method can not utilize cooling method for separation of methane and nitrogen from other hydrocarbon gas, thereby remarkable in economical benefits.
As previously mentioned, carried the active mechanism of liquid film to be considered to the Fick diffusion.Because the Fick diffusion coefficient in liquid is very insensitive to pressure, so can expect, the general answering pressure of the diffusion coefficient of measurement changes insensitive.In addition experimental results show that this point.Diffusion coefficient and total liquid film separation are generally insensitive to the variation of operating pressure in about 160～890kpa scope.
Be familiar with this technical staff on described principle, can carry out many other changes and improvements and can not run counter to principle of the present invention.Therefore it should be clearly know that disclosed principle only is an illustrative in specification, does not constitute limitation of the scope of the invention.
Claims (10)
1, a kind of liquid-film method, be used for gas stream is separated into infiltration gas stream that mainly has low balance K value and the gas stream that mainly has higher balance K value, it is characterized in that: input gas stream is contacted with the liquid film that is supported, above-mentioned liquid film has and the upstream side of input air-flow contact and opposite downstream, above-mentioned input air-flow and above-mentioned liquid film remain on the operating pressure and the temperature of the input air-flow dew point in the liquid/gas two phase region that quite approaches phase boundary, thereby in the input air-flow, produce cohesion, for liquid film provides liquid, porous is not discharged from the upstream side of liquid film by the gas flow that mainly has higher balance K value of liquid film, and porous is crossed the permeating airflow of the gas that mainly has low balance K value of liquid film and then discharged from the downstream of liquid film.
2, according to the described liquid-film method of claim 1, it is characterized in that: add a kind of compound in the input air-flow, the amount of its adding should be enough to make above-claimed cpd to provide agglomeration liquid for liquid film.
3, according to the described liquid-film method of claim 2, it is characterized in that: come separation of methane and hydrogen by add a kind of hydrocarbon that has four carbon atom at least in the input air-flow of methane and hydrogen, the addition of hydrocarbon should be enough to make this hydrocarbon to provide agglomeration liquid for liquid film.
4, according to the described liquid-film method of claim 1, it is characterized in that: by hydrocarbon input air-flow being contacted with the hydrocarbon liquid film that is supported and above-mentioned hydrocarbon input flow separation being become mainly to have the permeating airflow of the hydrocarbon gas that hangs down balance K value and the hydrocarbon gas air-flow that mainly has higher balance K value.
5, according to the described liquid-film method of claim 4, it is characterized in that: utilize a kind of nytron liquid to soak into support, form initial liquid film thus, this hydrocarbon is from kerosene, the alkane that has ten carbon atoms at least, vaseline, oily type paraffin wax and C
7+Select in this group material of the high crude oil of content.
6, according to claim 4 or the described liquid-film method of claim 5, it is characterized in that: the permeating airflow of the hydrocarbon gas downstream from liquid film is purged out with a kind of purge gas.
7, according to the described liquid-film method of any one claim in the claim 1 to 6, it is characterized in that: be adjusted in the input air-flow in the liquid/gas two phase region of phase boundary and the operating temperature and the pressure of liquid film, so that when input air-flow component changes, can keep the cohesion amount that needs at the upstream side of liquid film.
8, according to the described liquid-film method of any one claim in the claim 1 to 7, it is characterized in that: above-mentioned liquid film is supported less than the support of 5000 dusts substantially by a kind of mesh size.
9, according to the described liquid-film method of any one claim in the claim 4 to 6, it is characterized in that: by a kind of hydrocarbon that has four carbon atom at least being added the input air-flow that separates ethane and ethene in the input air-flow, the addition of above-mentioned hydrocarbon should be enough to make this hydrocarbon to provide agglomeration liquid for liquid film.
10, according to the described liquid-film method of claim 4, it is characterized in that: by hydrocarbon input air-flow contact with hydrocarbon liquid film on a support and above-mentioned hydrocarbon input flow separation become mainly to comprise the air-flow of methane and mainly comprising permeating airflow than the alkane hydrocarbon gas of methane weight, above-mentioned input air-flow comprises methane and heavier alkane, forms initial above-mentioned liquid film by soaking into support with the hydrocarbon liquid that has six carbon atom at least.
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| CN 90107832 CN1060040A (en) | 1990-09-17 | 1990-09-17 | The liquid-film method of divided gas flow |
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| CN 90107832 CN1060040A (en) | 1990-09-17 | 1990-09-17 | The liquid-film method of divided gas flow |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780375B (en) * | 2008-04-30 | 2013-09-18 | 赛尔格有限责任公司 | A contained liquid membrane contactor and a method of manufacturing the same |
| CN108744861A (en) * | 2018-07-13 | 2018-11-06 | 中山医学大学 | Gas fractionation unit and method |
| CN112867551A (en) * | 2018-10-19 | 2021-05-28 | 依姆泰克斯膜公司 | Replenishment of membranes with liquid substances in a multi-module system |
-
1990
- 1990-09-17 CN CN 90107832 patent/CN1060040A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780375B (en) * | 2008-04-30 | 2013-09-18 | 赛尔格有限责任公司 | A contained liquid membrane contactor and a method of manufacturing the same |
| CN108744861A (en) * | 2018-07-13 | 2018-11-06 | 中山医学大学 | Gas fractionation unit and method |
| CN112867551A (en) * | 2018-10-19 | 2021-05-28 | 依姆泰克斯膜公司 | Replenishment of membranes with liquid substances in a multi-module system |
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