WO2009030767A1 - Procédé et système de production de constituants gazeux et de constituants condensables - Google Patents

Procédé et système de production de constituants gazeux et de constituants condensables Download PDF

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Publication number
WO2009030767A1
WO2009030767A1 PCT/EP2008/061821 EP2008061821W WO2009030767A1 WO 2009030767 A1 WO2009030767 A1 WO 2009030767A1 EP 2008061821 W EP2008061821 W EP 2008061821W WO 2009030767 A1 WO2009030767 A1 WO 2009030767A1
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WIPO (PCT)
Prior art keywords
gas
flow path
permeable
byproduct
separation membrane
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PCT/EP2008/061821
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English (en)
Inventor
Kazuo Kitsukawa
Naohiko Yamashita
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L'air Liquide, Société Anonyme pour l'Étude et l'Exploitation des Procédés Georges Claude
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Application filed by L'air Liquide, Société Anonyme pour l'Étude et l'Exploitation des Procédés Georges Claude filed Critical L'air Liquide, Société Anonyme pour l'Étude et l'Exploitation des Procédés Georges Claude
Publication of WO2009030767A1 publication Critical patent/WO2009030767A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/13—Use of sweep gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/14—Pressure control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/022—Reject series

Definitions

  • the present invention relates to a method and a system of producing gaseous components and condensable components. More specifically the present invention relates to a method and a system of producing gaseous components and condensable components by separating and collecting specific gaseous components from multiple-component gas mixtures, using the separation property of a selectively permeable gas separation membrane and the vapor- liquid separation property based on the differences between the condensation temperatures of each component.
  • a cascade cycle as the one shown in Figure 10 is efficient in case it is necessary to produce comparatively high pressure hydrogen gas and comparatively low pressure hydrogen gas.
  • a combination of two gas separation membranes 201 (the first gas separation membrane 201a and the second gas separation membrane 201 b) is used.
  • the feed gas g1 merges with the permeable gas g2aa from the second gas separation membrane 201 b, and it is supplied to the first gas separation membrane 201 a after compression.
  • the permeable gas g2a is generated through the first gas separation membrane 201 a, and the residual gas g2b is fed to the second gas separation membrane 201 b as a feed gas.
  • FIG. 10 shows a structural example for cases in which the permeable gas g2aa from the second gas separation membrane 201 b is reused; however, it is possible to extract the permeable gas g2a as a high pressure product gas, and the permeable gas g2aa as a low pressure product gas.
  • FIG. 11 a system for separating and collecting enriched nitrogen gas from air is given as an example parallel cycle.
  • two hollow fiber separation membrane modules 312 and 313 are used in parallel, the supply gas is fed to modules 312 and 313 respectively after the pretreatment process had been completed, and the enriched nitrogen gases obtained from the hollow fiber separation membrane modules 312 and 313 respectively are merged and led towards the product gas exit 324.
  • the air taken in from air intake port 301 is supplied to compressor 303 after such substances as suspended particles in the air are removed at dust filter 302.
  • the air pressurized here is led from the gas supply port of hollow fiber separation membrane modules 312 and 313 to the supply side of the membranes.
  • the permeated permeable gas flows through the permeation side of the membranes and is discharged to outside the system as permeable gas discharge flow via the permeable gas discharge port of the modules and after its flow rate is reduced at flow rate regulator valves 316 and 317 located midway through the piping (See for example the Japanese Patent Application No. 2002-35530).
  • the system as shown in Figure 11 represents cases in which enriched nitrogen gas is collected as the product gas
  • the permeable gas discharge flow is enriched oxygen gas and therefore it is also possible to collect this as the product gas.
  • the present invention focuses on the avoidance of liquefaction accompanying the concentration of condensable components in the gas on the primary side of the gas separation membrane.
  • the gas in the (nearest) residual gas port is the most liquefiable because the concentration of the condensable components passes together with the permeability. Consequently, the dew-point temperature under the pressure of the gas in the residual gas port becomes important, and liquefaction does not occur in the gas on the primary side of the gas separation membrane provided the dew-point temperature is low in comparison with the temperature of the gas at the gas separation membrane.
  • the gas separation membrane taking into consideration such aspects as the fluctuation of the feed gas mixture and of the operation conditions, it is preferable to set slightly lower gas temperature (for example, 10 0 C) at the gas separation membrane, and standard values for the dew-point temperature.
  • the pressure shortly after the residual gas port of the gas separation membrane is referred to hereafter as “residual gas pressure”
  • the dew-point temperature under the residual port pressure shortly after the residual gas port of the gas separation membrane is referred to as “residual gas flow rate”
  • the pressure and the flow rate of the permeable gas are referred to as "permeable gas pressure” and “permeable gas flow rate” respectively.
  • the aim of the present invention is to provide a method and a system of producing gaseous components and condensable components that guarantee the desired gas product having the desired purity and condensable components by collecting gaseous components and condensable components from feed gas containing multiple components, and a high recovery rate while avoiding the liquefaction of the condensable components in the primary side gas of the gas separation membrane through an efficient multipurpose method.
  • the aim of the present invention is particularly to yield an even higher recovery rate through the amount reduction process.
  • recovery rate means the rate of the total desired components (highly permeable gas) flow rate in the product gas as against the desired components flow rate in the feed gas; moreover, it includes cases when final residual gas is used as byproduct.
  • the present invention relates to a method of separating a feed gas containing multiple components, including a separation step using one or several selectively gas permeable membrane(s) and one or several steps consisting of a vapor-liquid separation using the differences in condensability of at least one component, said method generating:
  • component A Highly permeable and non-condensable components
  • component B semi-permeable and condensable components
  • semi-permeable and non-condensable components or components containing a reduced amount of the component
  • Component A consists of one or several highly permeable gases, such as, but not limited to, hydrogen, oxygen and/or nitrogen.
  • Component B consists of one or several less permeable, condensable gases, such as, but not limited to, water and/or organic compounds. "Highly permeable”, “semi permeable” and “condensable” can have a relative meaning, in the sense that component A is more permeable than component B through the membranes that are considered and chosen for the purpose of the invention and component B is more easily condensed than component A in an industrial vapor-liquid separation.
  • a method using the separation property by means of a selectively gas permeable separation membrane, and a method using the vapor-liquid separation property based on the differences between the condensability of each component are methods for securing the desired purity and recovery rate, that were previously often used separately. Moreover, even when these methods are combined, the method of processing the gas processed by using the vapor-liquid separation property as preprocessing by using the separation property of the gas separation membrane, or the reverse method thereof are used; however, any one of them was considered as the main method, while the other one was considered as an auxiliary method.
  • the present invention aims at increasing the recovery rate of the condensable and semi-permeable components by using the fact that the component B in the residual gas on the gas separation membrane concentrates, and by installing the assembly consisting of the cooling unit and the vapor-liquid separation unit before or after the gas separation membrane.
  • the present invention limits the residual gas dew-point temperature, has the component A left to some degree in the residual gas concentrated in the byproduct gas by the cooling and vapor-liquid separation of the residual gas in order to avoid the liquefaction on the primary side of the gas separation membrane, and aims at increasing the recovery rate of the permeable gas components by adding part of the byproduct gas to the secondary side flow path of the gas separation membrane.
  • gas separation membrane does not refer only to each inflow and outflow of supply gas, permeable gas and residual gas using one membrane module, but also to the combined inflow and outflow of each supplied gas, permeable gas and residual gas provided by using the necessary number of multiple membrane modules arranged in parallel lines.
  • secondary side flow path of the gas separation membrane includes any of the following flow paths: the flow path and the space between the permeable side of the gas separation membrane inner membrane element, as well as the permeable gas discharge flow channel.
  • Condensable components are those components which possess condensability properties as against condensation management and are not restricted to easy or difficult permeability as against gas separation membrane.
  • Highly permeable and non-condensable component A is that component which is highly permeable as against gas separation membrane and is non-condensable as against condensability management, more specifically, in the embodiments below, it refers to, for example, the hydrogen wherein a mixture of hydrogen, methane, butane and pentane is present in the feed gas.
  • “Semi-permeable and condensable component B” is that component which is semi-permeable as against gas separation membrane and is condensable as against condensability management, namely the above- mentioned butane and pentane. Moreover, in the present invention, even when the source gas contains permeable and condensable components in small quantities (for example, the feed gas moisture content in the embodiments below), the result is essentially the same. Consequently, the present invention will make annotations on such cases. Moreover, “pressure and connected process values” refer to the process value changes following the pressure changes, being possible to raise either the quantity of the residual gas as against primary pressure or the distribution of the permeable gas as against secondary pressure. The same applies hereinafter.
  • the present invention also relates to a gas separation system including a selectively gas permeable membrane and a vapor-liquid separating unit based on the differences in condensability of each component, and generating a permeable gas rich in highly permeable and non-condensable component A obtained from the gas separation membrane, a byproduct liquid rich in semipermeable and condensable component B obtained from the vapor-liquid separation unit, and byproduct gas lean in the component B, and a system for producing gaseous components and condensable components characterized in that it contains at least the following elements:
  • a producing system which embodies the above-described producing method necessarily includes a gas separation membrane and the elements (a) - (k 1 ) constituted of a cooling unit and a vapor-liquid separation unit, as well as an element for adding the added gas to the secondary side flow path of the gas separation membrane.
  • component (m) a product gas flow path for connecting and making the added gas flow path and the permeable gas flow path
  • component A present in the residual gas to a certain level, is condensed in the byproduct gas by residual gas cooling and vapor-liquid separation, thus being possible to measure the increase in the permeable gaseous components recovery rate by adding part of the byproduct gas to the permeable gas.
  • the purity of permeable gas at separation membrane exceeds the standard value, the high recovery rate of the permeable gaseous components can be preserved by efficiently using part of the byproduct gas as permeable gas, while avoiding the liquefaction on the gas separation membrane primary side.
  • the present invention also relates to a gas separation system including a selectively gas permeable membrane and a vapor-liquid separating unit based on the differences in condensability of at least one component, generating a permeable gas rich in highly permeable and non-condensable component A obtained from the gas separation membrane, a byproduct liquid rich in semipermeable and condensable component B obtained from the vapor-liquid separation unit, and a byproduct gas containing a reduced amount of component B, said system being characterized in that it contains at least the following elements:
  • the manufacturing system which embodies the above-described producing method necessarily includes a gas separation membrane and the elements (a) - (k 1 ) constituted of a cooling unit and a vapor-liquid separation unit, as well as an element for adding the added gas to the secondary side flow path of the gas separation membrane.
  • the present invention provides (n) "the added gas entry that connects to the added gas flow path on the secondary side of the gas separation membrane" as such a component.
  • the pressure of component A on the permeable side of the gas separation membrane decreases, and the permeability property of the component A can be increased.
  • the abovementioned systems are characterized in that the following elements are located on the feed gas flow path: (aa) a first cooling unit
  • the cooling means and the vapor-liquid separation means are located after the gas separation membrane, and byproduct gas is added to the permeable gas; however, it is preferable for the functions and results obtained by means of such a configuration to preprocess the feed gas according to its properties.
  • the first cooling unit and the first vapor-liquid separation unit for collecting the component B, or the heating unit aiming at preventing the liquefaction due to the raise in concentration of the component B in the residual gas are installed on the upstream path side of the gas separation membrane, making it possible to aim at increasing the recovery rate of the permeable gas and of the condensable components.
  • the abovementioned methods are characterized in that, especially for turndown operation, either the primary pressure of the aforementioned membrane, the secondary pressure of the aforementioned membrane or the process values connected with said pressure is adjusted according to the degree of turndown, and wherein the flowrate of the added gas is also adjusted according to the degree of turndown.
  • the present invention aims at preventing the liquefaction of the condensable components, and at maintaining the desired product gas purity and recovery rate by adjusting either the primary pressure and the secondary pressure of the gas separation membrane or the process values connected with said pressures according to the degree of amount reduction to preserve the purity of the product gas, and by controlling the added gas flow rate according to the degree of amount reduction.
  • the abovementioned methods are characterized in that the gas separation membrane consists of several stages of gas separation membranes forming a cascade, the residual gas of one separation membrane being sent to the following gas separation membrane in the cascade.
  • gas separation membrane includes several stages of gas separation membrane forming a cascade, the residual gas flow path of one gas separation membrane being connected to the feed gas flow path of the next gas separation membrane.
  • the cascade cycle can preserve the given product purity and the recovery rate by using a multiple phase gas separation membrane and by making each permeable gas a product gas, even when the membrane area is comparatively small. Namely, because permeable gas is found in relatively large quantities in the residual gas of the former gas separation membrane and is provided in a gas separation membrane, it is possible to efficiently recover the condensable components which condense. Beside this general benefit of the cascade cycle, the present invention makes it possible to obtain product gas by adding the condensed gas obtained as above to permeable gas and to obtain a high- recovery rate desired component purity in the product gas even as against small quantities. In such cases, the addition can be done as against any of the permeable gas multiple phases.
  • the present invention is not restricted to the configuration examples mentioned below, a large number of deformations or dilatations being possible as a result of the combination of the gas separation membrane above-mentioned general characteristics.
  • FIG. 1 shows the basic configuration example of the inventive gaseous mixture separation system (the first configuration example is referred to as "the inventive system 1").
  • this systems consists of the feed gas flow path Uo, the gas separation membrane S, permeable gas flow path T1 , residual gas flow path R1 , byproduct gas flow path G2, byproduct liquid flow path L2, added gas flow path Fa, product gas flow path A1 , cooling unit C2 and vapor-liquid separation unit D2 installed on the residual gas flow path G1 , pressure adjustment means PCrI (pressure control valve PCV1 and pressure regulator PC1 ) installed on the byproduct gas flow path G2, liquid surface detection unit LC2 and control valve LCV2 installed on the byproduct liquid flow path L2, flow path adjustment means FCbI (flow path control valve FCV1 and flow path controller FC1 ) installed on the added gas flow path Fa, and control unit (not illustrated).
  • PCrI pressure control valve PCV1 and pressure regulator PC1
  • FCbI flow path control valve FCV1 and flow path controller FC1
  • the analysis port APo of the feed gas, the analysis port AP1 of the added gas, and the analysis port AP3 of the product gas are provided to confirm performance of the gas producing process. It is also possible to install a concentration measurement means instead of the analysis ports. See details below.
  • the structure illustrated here shows a structure wherein the primary pressure P1 supplying the feed gas is controlled by means of the pressure adjustment means PCrI installed on the byproduct gas flow path G2; however, the feed gas flow path Uo, the residual gas flow path R1 , or another by-pass flow path can be added to the pressure adjustment means PCrI ; the present invention is in no way limited to these structures.
  • Purified gas or crude gas that has undergone a purification treatment is preferably supplied as the feed gas; in concrete terms, purified air, purified naphtha cracked gas, purified reformed gas, purified water gas, or purified natural gas is applicable.
  • the supply conditions for the feed gas are usually ambient temperature and the flow rate of these gases ranges from 1 ,000 to 100,000 [Nm 3 /h].
  • the pressure conditions are different depending on the intended use of the permeable gas; however, a pressure up to 1-50 [bar(abs)] can be applied.
  • the optimal raw material and capacity (surface area) of the gas separation membrane S is chosen depending on the types of feed gas or permeable gas.
  • the raw materials that can be used for the gas separation membrane S include, for example, polyethylene (PE), polypropylene (PP), silicon gum, polysulfone, cellulose acetate, polyaramide (PA), and polyimide (Pl).
  • PE polyethylene
  • PP polypropylene
  • PA polyaramide
  • Pl polyimide
  • concentration measurement means can also be used for control, as described below.
  • Concentration measurement means having highly selective analyzer are preferred for the desired components, namely for the product gas components, and a device that can be relied upon for continuous analysis is preferred.
  • an analyzer that does not cause chemical modifications of the product gas is preferred.
  • a thermal conductivity analyzer can be used in case the components are hydrogen, and an infrared absorption spectrophotometer can be used in case of methane.
  • the process from the feed gas supplied to the gas separation membrane S of the inventive system 1 to the producing of final product gas and condensable component includes at least the following processes:
  • the primary pressure P1 is controlled, the permeable gas pressure and recovery rate are adjusted, and at the same time the dew-point temperature is adjusted; in addition, the added gas flow rate F1 is adjusted, and the product gas concentration and recovery rate are adjusted within the desired range.
  • the primary pressure P1 of the gas separation membrane S is controlled using the pressure control means PCrI installed on the byproduct gas flow rate G2; next, the added gas flow rate F1 is controlled using the flow path control means FCbI . It is also possible to control the added gas flow rate F1 based on the desired components concentration extracted from the analysis port AP3.
  • the feed gas contains the component B
  • the primary pressure P1 of the gas separation membrane S was kept at a constant level, on the one hand the recovery rate rises as above, and on the other hand the concentration of the permeable gas in the permeable gas decreases, while the component B in the gas on the primary side of the gas separation membrane S is concentrated and liquefaction may occur.
  • the primary pressure P1 was reduced according to the decrease of feed gas flow rate, the liquefaction of the component B in the gas on the primary side of the gas separation membrane S can be prevented because the pressure of the component B drops.
  • constant recovery rate can be maintained in the amount reduction process because the flow rates of the permeable gas and the residual gas respectively also change according to the flow rate of the feed gas.
  • the calculation of the amount reduction rate using the diode function for example, the primary pressure does not drop, until the predetermined amount reduction rate, and for the amount reduction rate beyond this value, there are cases when a method of decreasing the primary pressure P1 according to the amount reduction rate is preferred. Namely, by using a configuration or a method as the one described above, the size of the membrane module does not change even when the feed gas flow rate decreases, and it has become possible to stabilize the purity and the recovery rate of the desired product gas by means of a simple method.
  • the recovery rate increases when the primary pressure P1 and the secondary pressure P2 are kept at a constant value upon amount reduction; however, it is also possible to prevent liquefaction by controlling the increase of recovery rate by increasing the secondary pressure P2.
  • the analyzer in case a trustworthy analyzer is used, the analyzer is placed in the location of AP3, and the added gas flow rate F1 can be controlled so that the product purity after merging becomes the defined value.
  • the added gas flow arte F1 can also be controlled by the function of the degree of reduction (for example, the primary function or the polygonal line function). Details are not provided, however, in addition, using the concentration of the component A in the residual gas and the correlation function of the residual gas pressure, the method of avoiding the liquefaction on the primary side of the gas separation membrane (See patent Citation 2007-232918 A VERIFIER) is also efficient. The same applies to the other configuration examples below.
  • the second configuration example of the inventive gaseous mixture separation system (referred to hereafter as the inventive system 2) is shown in Figure 2
  • the method of adding part of the byproduct gas into the secondary side flow path of the gas separation membrane S consists from connecting the added gas flow path Fa to the added gas installation unit located on the permeable side (secondary side) of the gas separation membrane S, and mixing the added gas inside the gas separation membrane S with the permeable gas. While mixing with the permeable gas, the mixture of added gas and permeable gas is extracted from the permeable gas flow path T1 passing though the secondary side.
  • the concentration of the component A is generally lower in the added gas than in the permeable gas; therefore, the component A becomes highly permeable when the added gas is introduced into the secondary side of the gas separation membrane S, because the pressure of the component A on the secondary side decreases. Namely, the recovery rate of the ingredient A gained, and the surface area of the gas separation membrane S can be reduced.
  • the primary side flow feed gas flow path Uo - regeneration gas flow path G1
  • the secondary side flow (added gas flow path Fa - permeable gas flow path T1 ) are passing via the membrane module (not shown) from opposite sides; however, cases of both flows passing orthogonally, as counter-flows, or co-current flows are possible.
  • Counter-flows are preferably used for the inventive system 2.
  • For the primary side flow it is difficult to maintain the driving force of the permeation, because the concentration of the ingredient A decreases as the flow comes closer to the outlet. From the perspective of redressing this situation, if the counter-flow style is used, it is preferable to introduce the added gas having a low concentration of component A from this position, because the inlet on the secondary side flow is placed on the opposite side of the outlet of the primary side flow.
  • the heating means (heating unit H) is preferably installed on the flow path supplying the added gas to the gas separation membrane S.
  • the added gas is not mixed directly with the permeable gas, but introduced into the added gas entry Sf of the gas separation membrane S after heating with the heating unit H.
  • the byproduct gas forming the added gas is cooled in the second cooling unit C2 and the second vapor-liquid separation unit D2, and heating is preferable for the gas separation membrane S to function at the adequate temperature.
  • the added gas contains liquefied mist
  • the gas separation membrane S deteriorates by itself.
  • the added gas contains condensable components, maximum vapor pressure is obtained at cooled temperature in the second cooling unit C2; therefore, liquefaction can occur at ambient temperature, danger can be avoided by heating, and gas separation can be carried out under safe conditions.
  • the inventive system 2 comprises the aforementioned processes (1 )-(9) and the processes below into the process of producing gaseous components and condensable components.
  • the flow rate F1 of the added gas is controlled, and the product gas concentration and recovery rate are adjusted within the desired range, in a way similar to that of the above-described first configuration example. .
  • FIG 3 shows the third configuration example of the inventive gaseous mixture separation system (referred to hereafter as "the inventive system 3").
  • this system is similar to the first configuration example; however, in order to enable primary processing of the feed gas, this system also comprises any of the following units located between the feed gas flow path Uo and the gas separation membrane S: first cooling unit C1 , the first vapor-liquid separation unit D1 , the first byproduct gas flow path G1 , the heating unit H, the first byproduct liquid flow path L1 , the first byproduct gas flow path G1 , and the first liquid surface liquid surface detection unit LC1 and the first control valve LCV1 installed on the first byproduct liquid flow path L1.
  • the byproduct gas flow path G2, the byproduct liquid flow path L2, the cooling unit C2 and the vapor-liquid separation unit D2, the liquid surface detection unit LC2 and the control valve LCV2 of the first configuration example are hereafter each preceded by "the second, as for example the second byproduct gas flow path G2 and so on.
  • the inventive system 3 is preferably used in order to prevent occurrence of mist in case the feed gas contains an even larger amount of component B.
  • the concentration of the ingredient A in the gas supplied to the gas separation membrane S can be increased and the concentration of the component B can be decreased through the primary cooling process of the feed gas and the primary vapor-liquid separation process, and the load of the selective separation process through the gas separation membrane S, the secondary cooling process of the residual gas, and the secondary vapor-liquid separation process can be reduced.
  • the concentration of the ingredient A in the permeable gas also increases, part of the second byproduct gas containing a smaller amount of the component B after the secondary vapor-liquid separation process is diverged and mixed with the permeable gas as added gas, yielding higher recovery rate of the ingredient A.
  • the point of the primary processing of the feed gas is that it is in no way restricted directly in front of the primary cooling unit C1 as shown in Figure 3, but depending on the temperature of the feed gas or on the dew-point temperature thereof, it can be placed in the locations marked by the broken lines a - c, namely, a: between the first cooling unit C1 and the first vapor-liquid separation D1 , b: between the first vapor-liquid separation unit D1 and the heating unit H, or c: between the heating unit H and the gas separation membrane S.
  • Another processor can be used in cases such as difficult maintenance of the desired supply pressure combined with the properties of the gas separation membrane S.
  • the heating means are preferably installed on the flow path supplying the feed gas to the gas separation membrane S.
  • Gas separation must be carried out according to the characteristics and use of the gas separation membrane, and at the adequate temperature.
  • the gas separation membrane S may deteriorate by itself.
  • the feed gas comprises condensable components, liquefaction can occur at ambient temperature; when these condensable components are semi-permeable (component B), the component B in the gas on the primary side (impermeable side) of the gas separation membrane concentrate and liquefaction can occur.
  • the inventive system 3 comprises either one or a combination of the processes below, as part of the process of producing gaseous components and condensable components.
  • the added gas flow rate F1 is adjusted, and the product gas concentration and recovery rate are adjusted within the desired range, in a way similar to that described for the first configuration example.
  • the alternative embodiment of the third configuration example is shown in Figure 4. Namely, the specific configuration is similar to the third configuration example; however, in addition to said configuration example, the pressure adjustment means PCro (the pressure control valve PCVo and the pressure regulator PCO) are installed on the first byproduct gas flow path G1. In the reduction of amount of feed gas, it becomes possible to control the pressure of the first vapor-liquid separation unit D1 independently of the primary pressure of the gas separation membrane S, and it also become possible to control the even higher pressure. Moreover, this type of configuration comprising the third configuration example can also be applied to the second configuration example, yielding similar effects and functions.
  • the pressure adjustment means PCro the pressure control valve PCVo and the pressure regulator PCO
  • FIG. 5 shows the forth configuration example of the inventive gaseous mixture separation system (referred to hereafter as "the inventive system 4").
  • this system is similar to the first configuration example; however, multiple stage gas separation membrane is used, the first residual gas flow path R1 of the former stage of the first gas separation membrane S1 is connected to the upper flow path side of the latter stage of the second gas separation membrane S2, and a cascade connection forms.
  • the first residual gas flow path R1 of the first gas separation membrane S1 to the supply gas flow path of the second gas separation membrane S2
  • the first permeable gas is extracted from the first permeable gas flow path T1 , and it becomes possible to extract the second permeable gas is extracted from the second permeable gas flow path T2.
  • the configuration in Figure 5 allows the unification of the added gas flow path Fa, separated from the byproduct gas flow path G2, with the first permeable gas flow path T1 , so as to mix the added gas with the first permeable gas.
  • the cascade cycle is often used because it has the advantage of yielding raised recovery rate in case multiple-purity permeable gas is obtained by changing permeable gas pressure of each stage and the material of the membrane in the gas separation membrane. At this point, the concentration of the component B in the second residual gas is controlled and it is possible to efficiently prevent liquefaction, by selecting the surface are of the first gas separation membrane S1 and the second gas separation membrane S2.
  • concentrated gas is added to the permeable gas, and it can be extracted as the product gas; also, in the amount reduction process, it becomes possible to form the desired component concentration in the product gas with a high recovery rate. Moreover, it becomes possible to react flexibly to the modifications in process conditions during amount reduction.
  • Figure 5 illustrates the case wherein the permeable gas of the first gas separation membrane S1 is mixed with the added gas; however, the mixture of the permeable gas and the added gas is in no way limited to this situation; addition is possible to any of the permeable gases of the multiple stages. Moreover, using the cascade system, by controlling the primary pressure of the gas separation membrane of each stage to a sequentially lower value, it becomes possible to raise the recovery rate of the permeable gas.
  • FIG. 6 Alternative embodiments of the forth configuration example are shown in Figure 6 and Figure 7. Namely, this system is similar to the forth configuration example; however, a system comprising the pressure adjustment means PCr2 (pressure control valve PCV2 and pressure controller PC2) installed on the first residual gas flow path R1 is shown in Figure 6.
  • the pressure adjustment means PCr2 pressure control valve PCV2 and pressure controller PC2
  • PCro pressure control valve PCVo and pressure controller PCO
  • the pressure of the first vapor-liquid separation unit D1 can be controlled independently of the primary pressure of the first and second gas separation membranes S1 and S2, and in addition it become possible to control the even higher pressure.
  • the mixing point of the feed gas and the circulating gas in Fig, 7 is that as shown can be placed in the locations marked by the broken lines a - b, namely, (a) between the first cooling unit C1 and the first vapor-liquid separation D1 , (b) between the first vapor-liquid separation unit D1 and the pressure adjustment means PCro.
  • Figure 8 shows the fifth configuration example of the inventive gaseous mixture separation system (referred to hereafter as "the inventive system 5").
  • This system is similar to the second configuration example; however, the configuration in Figure 8, allows the unification of the added gas flow path Fa with the added gas installation unit Sf located on the permeable side (secondary side) of the second gas separation membrane S2, so as to mix the added gas with the first permeable gas inside the second gas separation membrane S2.
  • higher purity and recovery rate of the ingredient A can be secured by introducing part of the byproduct gas as added gas into the secondary side of the second gas separation membrane S2.
  • Figure 8 illustrates the case wherein the permeable gas and the added gas of the second gas separation membrane S2 are mixed; however, the mixture of the permeable gas and the added gas is in no way limited to this situation; gas can be added against permeable gas at any stage.
  • gas can be added against permeable gas at any stage.
  • using the cascade style by controlling the primary pressure of the gas separation membrane in each stage to a lower value, it becomes possible to raise the recovery rate of the permeable gas.
  • the effects and functions disclosed in the above-described "alternative embodiment of the inventive system 4" can be applied to the inventive system 5, yielding similar technical results.
  • the hydrogen gas producing process is set with respect to the above- described configuration examples, and the results of the numerical analysis for the purity and recovery rate of the permeable gas are shown hereafter.
  • the temperature of the feed gas at the entrance of the gas separation membrane was 90 0 C.
  • the dew-point temperature of the residual gas at the exit of the gas separation membrane was ⁇ 80 0 C as a general rule.
  • the temperature was reduced to 40 0 C using the water cooling method as the first and second cooling units.
  • the pressure of the permeable gas was 10 bar (abs) at the exit of the gas separation membrane.
  • the pressure of the permeable gas in the first and second gas separation membranes was equal, also in case of the cascade system.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • Embodiment 1 The analysis results are shown in the Embodiments 1 to 3.
  • a case was analyzed with the system using the one stage gas separation membrane as shown in Figure 1 , wherein the flow path of added gas (simulating the case wherein the hydrogen concentration of the product was determined with an analyzer) was controlled so that the product purity was near 95% of the standard value.
  • the residual gas pressure of the gas separation membrane of the feed gas in Table 1 was modified by means of the primary equation of the degree of amount reduction, and reduction of the amount was attempted.
  • the surface area of the gas separation membrane was set so that the dew-point temperature at the residual gas exhaust port was approximately 80 0 C when the feed gas flow rate was 100%.
  • the recovery rate increased in an outstanding way with the amount reduction.
  • the recovery rate decreased to 79.39% in case the added gas flow rate was set to 0 when the feed gas flow rate was 100%.
  • condensation did not occur even when the feed gas was cooled to a temperature of 40 0 C.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a case was analyzed with the cascade system using the two stage gas separation membrane as shown in Figure 5, wherein the residual gas pressure of the gas separation membrane of each stage of the feed gas in Table 1 and the added gas flow rate was modified by means of the primary equation of the degree of amount reduction, and the amount was reduced.
  • the surface areas of the first and second gas separation membranes were adjusted to 100% and 50% of Embodiment 1 respectively.
  • FIG. 1 is an explanatory drawing illustrating the basic configuration example of the inventive producing system.
  • FIG. 2 is an explanatory drawing illustrating the second configuration example of the inventive producing system.
  • FIG. 3 is an explanatory drawing illustrating the third configuration example of the inventive producing system.
  • FIG. 4 is an explanatory drawing illustrating the alternative embodiment of the third configuration example of the inventive producing system.
  • FIG. 5 is an explanatory drawing illustrating the forth configuration example of the inventive producing system.
  • Figure 6 is an explanatory drawing illustrating the alternative embodiment of the fourth configuration example of the inventive producing system.
  • FIG. 7 is an explanatory drawing illustrating the alternative embodiment of the fourth configuration example of the inventive producing system.
  • FIG. 8 is an explanatory drawing illustrating the fifth configuration example of the inventive producing system.
  • FIG. 9 is an explanatory drawing illustrating the basic configuration example of the conventional producing system.
  • FIG. 10 is an explanatory drawing illustrating another configuration example of the conventional producing system.
  • Figure 11 is an explanatory drawing illustrating yet another configuration example of the conventional producing system.
  • G1, G2 (first, second) byproduct gas flow path
  • R1, R2 (first, second) residual gas flow path

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

Procédé conçu pour séparer un gaz d'alimentation contenant plusieurs constituants. Ce procédé comprend une étape de séparation au moyen d'une ou de plusieurs membranes sélectivement perméables au gaz et une ou plusieurs étapes comprenant une séparation vapeur-liquide utilisant les différences de condensabilité d'au moins un constituant. Ce procédé permet de produire un gaz perméable riche en constituant A extrêmement perméable et non condensable, un liquide dérivé riche en constituant B semi-perméable et condensable, et un gaz dérivé pauvre en constituant B obtenu après séparation vapeur-liquide. Ce procédé est caractérisé en ce qu'il comprend au moins les étapes suivantes consistant (1) à acheminer le gaz d'alimentation à la membrane de séparation de gaz (S2), (2) à régler soit la pression primaire de la membrane de séparation de gaz soit les valeurs de traitement liées à ladite pression, (3) à séparer le gaz d'alimentation en un gaz perméable et un gaz résiduel (R2) au moyen de la membrane de séparation de gaz, (4) à extraire le gaz perméable riche en constituant A susmentionné en tant que gaz produit, (5) à extraire le gaz résiduel riche en gaz semi-perméable, (6) à refroidir le gaz résiduel et à réaliser une séparation vapeur-liquide (D2) qui débouche sur un liquide dérivé riche en constituant B susmentionné et sur un gaz dérivé pauvre en constituant B, (7) à dériver une partie du gaz dérivé comme gaz ajouté, (8) à ajouter une partie du gaz ajouté soit à la voie d'écoulement côté secondaire (Sf) de la membrane de séparation de gaz.
PCT/EP2008/061821 2007-09-07 2008-09-05 Procédé et système de production de constituants gazeux et de constituants condensables WO2009030767A1 (fr)

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CN105561743A (zh) * 2014-10-14 2016-05-11 中国石油化工股份有限公司 一种用于合成气膜法脱碳的增湿缓冲系统

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KR101416192B1 (ko) 2013-03-25 2014-07-09 한국지질자원연구원 페이스트 ｐＨ를 이용한 오염된 토양의 최종 평형 ｐＨ의 현장 측정방법

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