# Patent

## Title
Method for processing fischer-tropsch off-gas

## Abstract

This invention concerns a method for recovering carbon monoxide and carbon dioxide from Fischer-Tropsch off-gas by feeding Fischer-Tropsch off-gas through a column comprising an adsorbent bed, and discharging effluent, optionally rinsing the column and the adsorbent bed by feeding carbon dioxide and discharging effluent until at least 60% of the carbon monoxide that was present in the bed is discharged, pressurizing the column and adsorbent bed with carbon dioxide, rinsing the column and the adsorbent bed by feeding carbon dioxide, until at least 60% of the methane and optionally an amount equal to at least 50% of the carbon dioxide present at the commencement of this rinsing step is discharged, rinsing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen, pressurizing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen. With this method a feed comprising at least 50 vol % carbon monoxide can be produced. Furthermore, methane and carbon dioxide at a high pressure can be recovered from the Fischer-Tropsch gas. This can be fed to a gasifier or a reformer. In a preferred embodiment a gas comprising at least 80 vol % hydrogen is produced as well.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a National Stage (§371) of International Application No. PCT/EP2013/078173, filed Dec. 31, 2013, which claims priority from European Application No. 12199833.0, filed Dec. 31, 2012, the disclosures of each of which are hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to a process for processing Fischer-Tropsch off-gas. Carbon dioxide and carbon monoxide, and optionally hydrogen, can be recovered from the off-gas in a very efficient way.
BACKGROUND OF THE INVENTION
The Fischer-Tropsch process can be used for the conversion of hydrocarbonaceous feed stocks into normally liquid and/or solid hydrocarbons (i.e. measured at 0° C., 1 bar). The feed stock (e.g. natural gas, associated gas, coal-bed methane, residual oil fractions, biomass and/or coal) is converted in a first step into a mixture of hydrogen and carbon monoxide. This mixture is often referred to as synthesis gas or syngas. The synthesis gas is fed into a reactor where it is converted over a suitable catalyst at elevated temperature and pressure into paraffinic compounds ranging from methane to high molecular weight molecules comprising up to 200 carbon atoms, or, under particular circumstances, even more.
The hydrocarbon products manufactured in the Fischer-Tropsch process are processed into different fractions, for example a liquid hydrocarbon stream comprising mainly C5+ hydrocarbons, and a gaseous hydrocarbon stream which comprises methane, carbon dioxide, unconverted carbon monoxide, unconverted hydrogen, and lower hydrocarbons. The gaseous hydrocarbon stream may also comprise nitrogen as the syngas sent to the Fischer-Tropsch reactor may contain some nitrogen.
The gaseous hydrocarbon stream is often referred to as Fischer-Tropsch off-gas. Fischer-Tropsch off-gas can be recycled to the syngas manufacturing or to the Fischer-Tropsch reactor. Sometimes lower hydrocarbons are removed before the off-gas is recycled. Lower hydrocarbons may be removed by decreasing the temperature of the off-gas and then applying a gas-liquid separation. However, when the off-gas is recycled to the syngas manufacturing or to the Fischer-Tropsch reactor, the components in the off-gas which do not take part in the Fischer-Tropsch reaction, such as carbon dioxide, nitrogen and methane, occupy reactor space. The components which do not take part in the Fischer-Tropsch reaction are also referred to as “inerts”.
The level of inerts in the Fischer-Tropsch reactor increases with increasing Fischer-Tropsch off-gas recycling. The pace of the build-up of inerts can be reduced by treating the off-gas before it is recycled. When the off-gas is passed through a pressure swing adsorption unit (PSA), it is normally possible to remove carbon dioxide and water from the off-gas. It is often possible to recover a hydrogen stream from the off-gas by means of a PSA unit; the hydrogen stream can be recycled to the Fischer-Tropsch reactor. Nevertheless, common commercial PSA units are often not designed to recover a carbon monoxide stream. And some common commercial PSA units result in a hydrogen stream comprising a significant amount of nitrogen. Therefore it is common to recycle only a relatively small part of the off-gas. One possibility is to recycle a part of the Fischer-Tropsch off-gas to one or more Fischer-Tropsch reactors while another part of the off-gas is used as fuel. A downside of this is that only a part of the carbon atoms of the hydrocarbonaceous feed stock is converted to the desired C5+ hydrocarbons.
U.S. Pat. Nos. 5,112,590 and 5,096,470 describe the separation of gases using specific PSA systems with a first PSA unit for producing hydrogen and a second PSA unit for producing carbon monoxide. Such systems may be useful for gas mixtures comprising a relatively high amount of hydrogen. Such systems are, however, not suitable for gas mixtures comprising a relatively low amount of hydrogen, e.g. less than 50 volume % calculated on the total gas mixture. Furthermore, in case of a gas feed comprising a significant amount of nitrogen such systems will not result in the product cuts as described. When, for example, pure hydrogen would be separated using the first PSA, nitrogen would contaminate the intermediate carbon monoxide stream in a system according to U.S. Pat. Nos. 5,112,590 or 5,096,470. The systems of U.S. Pat. Nos. 5,112,590 and 5,096,470 may therefore be suitable to treat a hydrogen-rich gas mixture exiting a steam methane reformer, but they are not suitable to treat a nitrogen-comprising hydrogen-lean off-gas of a Fischer-Tropsch process.
US20110011128 describes a PSA comprising system in which purified hydrogen is produced using a PSA, which may be a conventional co-purge H2 PSA unit. Such a system may be useful to a hydrogen-rich gas mixture exiting a steam methane reformer, but is not suitable to treat nitrogen comprising hydrogen-lean off-gas of a Fischer-Tropsch process.
US20040077736 mentions a process in which a liquid phase and a vapour phase are withdrawn from a hydrocarbons synthesis stage. In a vapour phase work-up stage, hydrocarbon products having 3 or more carbon atoms may be removed and the residual vapour phase may then pass to a PSA. Using the PSA first, second and optionally third gas components are separated. The first gas component comprises carbon monoxide and hydrogen. The second gas component comprises methane, and the optional third gas component comprises carbon dioxide. The first gas component is recycled to the hydrocarbon synthesis stage. US20040077736 does not provide details on the method PSA method used. A regular use of a normal PSA would result in a relatively low recovery of carbon monoxide in the first gas component, and a build-up of nitrogen in the reactor upon recycling the first gas component to the hydrocarbon synthesis stage.
US20080300326-A1 describes the use of a PSA method to separate Fischer-Tropsch off-gas. The method produces at least one gas stream comprising hydrogen, at least one gas stream mainly comprising methane, and at least one gas stream comprising carbon dioxide, nitrogen and/or argon, and hydrocarbons with at least 2 carbon atoms. The PSA used comprises at least three adsorbent beds: alumina, carbon molecular sieves or silicates, activated carbon, and optionally zeolite. The alumina is used to remove water. The carbon molecular sieves or silicates are used to adsorb carbon dioxide and partially methane. The activated carbon is used to adsorb methane and partially nitrogen and carbon monoxide. Zeolite may be used to adsorb nitrogen, argon and carbon monoxide. The product stream of the PSA mainly comprises hydrogen. The other gas streams are obtained during the decompression phase. Disadvantages of the method of US20080300326-A1 are at least the following. Nitrogen is only partially adsorbed in the PSA. This results in a build-up of nitrogen in the Fischer-Tropsch reactor when the hydrogen stream is used, i.e. recycled, as reactant gas. Also the methane stream comprises nitrogen and thus results in the build-up of nitrogen in the syngas, and thus in the Fischer-Tropsch reactor, when the methane stream is used for generating syngas. Another disadvantage of the method of US20080300326-A1 is that carbon monoxide is only recycled to the Fischer-Tropsch reactor in a limited amount. Carbon monoxide is present in the hydrogen stream and in the methane stream. Nevertheless, at least 50% of the CO initially present in the off-gas ends up in the third stream which is used as fuel.
There is a desire to recover both carbon dioxide and carbon monoxide from Fischer-Tropsch off-gas in an efficient way. The carbon dioxide and carbon monoxide could then, together or separately, be recycled to one or more units in a Fischer-Tropsch line-up. This would make it possible to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons. It is even more desired to additionally obtain a pure hydrogen stream from Fischer-Tropsch off-gas, which may be recycled to the Fischer-Tropsch reactor.
SUMMARY OF THE INVENTION
The invention provides a method for recovering carbon monoxide and carbon dioxide from a gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, said method comprising, in sequence, the following steps:

    (1) feeding a gas mixture through a column comprising an adsorbent bed,
    
        said gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture,
        the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
        with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 10 to 80 bar absolute (bar a), preferably 20 to 70 bar a, with pure hydrogen, or with a mixture of hydrogen and nitrogen, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until a carbon monoxide comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and
    
    
    (2) ceasing the feeding of the gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, and reducing the pressure in the column and the bed by about 5 to 25 bar a, preferably by 10-25 bar a, more preferably by 15-20 bar a; and
    (3) optionally rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 5 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until at least 60% of the carbon monoxide that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed;
    
    
    (4) pressurizing the column and adsorbent bed by about 5 to 25 bar a by feeding a gas comprising at least 95 vol % carbon dioxide,
    (5) rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide, through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 30 to 80 bar a, preferably 30 to 70 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until
        
            at least 60% of the methane that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed, and
            optionally an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed; and
        
        
    
    
    (6) ceasing the feeding of a gas comprising at least 95 vol % carbon dioxide, and reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
    (7) rinsing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed
    
        the column and bed being at a pressure in the range of 1 to 5 bar a, and
    
    
    (8) pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a mixture of hydrogen and nitrogen,
    whereby said method optionally further comprises the following steps:
    (A) feeding the effluent of step (1) through a column comprising an adsorbent bed, the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
    
        with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 20 to 80 bar absolute (bar a), preferably 30 to 70 bar a, with a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until a nitrogen comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and
    
    
    (B) ceasing the feeding of the effluent of step (1), and reducing the pressure in the column and the bed by about 2 to 5 bar a; and
    (C) further reducing the pressure in the column and the bed by about 2 to 5 bar a; and
    (D) reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
    (E) rinsing the column and adsorbent bed by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, through the column and adsorbent bed
    
        the column and bed being at a pressure in the range of 1 to 5 bar a, and
    
    
    (F) pressurizing the column and adsorbent bed to a pressure in the range of 5 to 50 bar a, preferably 10 to 45 bar a, more preferably 20 to 40 bar a by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, and
    (G) further pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen.


One advantage of the present invention is that the method is suitable to obtain a carbon-monoxide rich stream from Fischer-Tropsch off-gas in optional step (3). This carbon-monoxide rich stream can be recycled to the Fischer-Tropsch reactor. A recovery of CO of greater than 50% may be obtained.
The process is also suitable to recover unconverted hydrogen in an efficient way from the Fischer-Tropsch off-gas. Unconverted hydrogen may be recycled to a Fischer-Tropsch reactor.
Another advantage of the present invention is that the method is suitable to recover a gas comprising methane and carbon dioxide, and optionally carbon monoxide, from the Fischer-Tropsch off-gas in step (5), whereby this gas can be obtained at high pressure. When the gas comprising methane and carbon dioxide is recovered at a high pressure it can be fed to a gasifier or a reformer, for example an auto thermal reformer, without performing a recompression step.
The process of the present invention makes it possible to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons.
The invention is further illustrated in the accompanying drawings.



DRAWINGS
FIG. 1 shows an overview of the process steps of a preferred method according to the invention.
FIG. 2 shows an overview of the process steps of another embodiment of the method of the present invention.



DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to processing of off-gas obtained from a Fischer-Tropsch reactor in order to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons. When removed from a Fischer-Tropsch reactor, the Fischer-Tropsch off-gas is generally at a temperature in the range of 40-100° C., preferably in the range of 50-70° C. and at a pressure of 20-80 bar, preferably in the range of 50-70 bar.
Fischer-Tropsch off-gas is typically produced by a Fischer-Tropsch hydrocarbon synthesis process comprising the steps of:

    i) conversion of a (gaseous) hydrocarbonaceous feed to obtain synthesis gas (syngas);
    ii) catalytic conversion of the synthesis gas obtained in step i) using a Fischer-Tropsch catalyst into a Fischer-Tropsch product; and
    iii) separating the Fischer-Tropsch product of step ii) into at least one hydrocarbon product stream and a Fischer-Tropsch off-gas.


Suitably, syngas production methods include steam reforming of natural gas or liquid hydrocarbons and gasification of coal. Methods to convert (gaseous) hydrocarbonaceous feed into syngas include adiabatic oxidative reforming, autothermal reforming and partial oxidation. Preferably, hydrocarbonaceous feed is converted to syngas by partial oxidation at elevated temperature and pressure using an oxygen containing gas. Partial oxidation can take place according to various established processes. Catalytic as well as non-catalytic processes may be used. These processes include the Shell Gasification Process. A comprehensive survey of this process can be found in the Oil and Gas Journal, Sep. 6, 1971, pp 86-90.
The H2/CO ratio of the syngas is suitably between 1.5 and 2.3, preferably between 1.8 and 2.1. The catalysts used for the catalytic conversion of the mixture comprising hydrogen and carbon monoxide into hydrocarbons are known in the art and are usually referred to as Fischer-Tropsch catalysts. Preferably, the catalysts for use in the Fischer-Tropsch hydrocarbon synthesis process comprises as the catalytically active component cobalt. The catalytically active component is preferably supported on a porous carrier, e.g. silica or titania. If desired, the Fischer-Tropsch catalyst may also comprise one or more metals or metal oxides as promoters. Typically, the catalytic conversion may be effected at a temperature in the range of 150 to 350° C., preferably from 180 to 270° C. Typical total pressures for the catalytic conversion process are in the range of from 1 to 200 bar absolute, more preferably from 10 to 70 bar absolute.
Generally, the Fischer-Tropsch hydrocarbon product stream is separated from the Fischer-Tropsch off-gas by a gas/liquid separator.
The Fischer-Tropsch off-gas may comprise gaseous hydrocarbons, nitrogen, unconverted methane, unconverted carbon monoxide, carbon dioxide, hydrogen and water. The gaseous hydrocarbons are suitably C1-C5 hydrocarbons, preferably C1-C4 hydrocarbons, more preferably C1-C3 hydrocarbons. These hydrocarbons, or mixtures thereof, are gaseous at temperatures of 5-30° C. (1 bar), especially at 20° C. (1 bar). Further, oxygenated compounds, e.g. methanol, dimethylether, may be present.
In most cases the Fischer-Tropsh off-gas will contain 10-40 vol % hydrogen, preferably 15-35 vol % hydrogen, 20-65 vol % CO, preferably 30-55 vol % CO, 10-50 vol % CO2, especially 15-45 vol % CO2, and 10-55 vol % N2, especially 15-50 vol % N2, calculated on the total volume of the gas mixture. Depending on the syngas feed and the Fischer-Tropsch conditions the composition of the Fischer-Tropsch off-gas can vary. Obviously, the total volume of the gas mixture is 100 vol %.
The present invention provides a method for recovering carbon monoxide and carbon dioxide from a gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, said method comprising, in sequence, the following steps:

    (1) feeding a gas mixture through a column comprising an adsorbent bed,
    
        said gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture,
        the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
        with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 10 to 80 bar absolute (bar a), preferably 20 to 70 bar a, with pure hydrogen, or with a mixture of hydrogen and nitrogen, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until a carbon monoxide comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and
    
    
    (2) ceasing the feeding of the gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, and reducing the pressure in the column and the bed by about 5 to 25 bar a, preferably by 10-25 bar a, more preferably by 15-20 bar a; and
    (3) optionally rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 5 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until at least 60% of the carbon monoxide that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed;
    
    
    (4) pressurizing the column and adsorbent bed by about 5 to 25 bar a by feeding a gas comprising at least 95 vol % carbon dioxide,
    (5) rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide, through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 30 to 80 bar a, preferably 30 to 70 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until
        
            at least 60% of the methane that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed, and
            optionally an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed; and
        
        
    
    
    (6) ceasing the feeding of a gas comprising at least 95 vol % carbon dioxide, and reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
    (7) rinsing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed
    
        the column and bed being at a pressure in the range of 1 to 5 bar a, and
    
    
    (8) pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a mixture of hydrogen and nitrogen,
    whereby said method optionally further comprises the following steps:
    (A) feeding the effluent of step (1) through a column comprising an adsorbent bed, the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
    
        with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 20 to 80 bar absolute (bar a), preferably 30 to 70 bar a, with a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until a nitrogen comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and
    
    
    (B) ceasing the feeding of the effluent of step (1), and reducing the pressure in the column and the bed by about 2 to 5 bar a; and
    (C) further reducing the pressure in the column and the bed by about 2 to 5 bar a; and
    (D) reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
    (E) rinsing the column and adsorbent bed by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, through the column and adsorbent bed
    
        the column and bed being at a pressure in the range of 1 to 5 bar a, and
    
    
    (F) pressurizing the column and adsorbent bed to a pressure in the range of 5 to 50 bar a, preferably 10 to 45 bar a, more preferably 20 to 40 bar a by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, and
    (G) further pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen.


One advantage of the present invention is that the method is suitable to obtain a carbon-monoxide rich stream from Fischer-Tropsch off-gas in optional step (3). This carbon-monoxide rich stream can be recycled to the Fischer-Tropsch reactor. A recovery of CO of greater than 50% may be obtained.
The process is also suitable to recover unconverted hydrogen in an efficient way from the Fischer-Tropsch off-gas. Unconverted hydrogen may be recycled to a Fischer-Tropsch reactor.
Another advantage of the present invention is that the method is suitable to recover a gas comprising methane and carbon dioxide, and optionally carbon monoxide, from the Fischer-Tropsch off-gas in step (5), whereby this gas can be obtained at high pressure. When the gas comprising methane and carbon dioxide is recovered at a high pressure it can be fed to a gasifier or a reformer, for example an auto thermal reformer, without performing a recompression step.
The process of the present invention makes it possible to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons.
In a preferred embodiment of the present invention repeated cycles of steps (1) to (8) are performed. In a preferred embodiment step (3) is performed. Effluent from one step can be used as feeding gas in another step; this is especially advantageous when repeated cycles of steps (1) to (8) are performed.
The method may be performed using a single column comprising an adsorbent bed. Preferably several columns that comprise an adsorbent bed are used. When using more than one column, the columns are preferably connected in parallel. Preferably the repeated cycles of steps (1) to (8) are performed over each column. In a preferred embodiment at least one column is subjected to one step of the cycle while another column is subjected to another step of the cycle. The product of one column can be used in another column, for example for purge, pressurization or rinse. In one embodiment at least two columns comprising an adsorbent bed, preferably at least six columns comprising an adsorbent bed, are subjected to repeated cycles of steps (1) to (8). Preferably at most 21, more preferably at most 16, columns comprising an adsorbent bed are subjected to repeated cycles of steps (1) to (8).
The gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, preferably is a gaseous product from a Fischer-Tropsch reaction. In that case it may be referred to as Fischer-Tropsch off-gas. Fischer-Tropsch off-gas is typically produced by a Fischer-Tropsch hydrocarbon synthesis process comprising the steps of:

    i) conversion of a (gaseous) hydrocarbonaceous feed to obtain synthesis gas (syngas);
    ii) catalytic conversion of the synthesis gas obtained in step i) using a Fischer-Tropsch catalyst into a Fischer-Tropsch product; and
    iii) separating the Fischer-Tropsch product of step ii) into at least one hydrocarbon product stream and a Fischer-Tropsch off-gas.
    The off-gas obtained in step iii) may comprise gaseous hydrocarbons, nitrogen, unconverted methane, unconverted carbon monoxide, carbon dioxide, hydrogen and water. The gaseous hydrocarbons are suitably C1-C5 hydrocarbons, preferably C1-C4 hydrocarbons, more preferably C1-C3 hydrocarbons. These hydrocarbons, or mixtures thereof, are gaseous at temperatures of 5-30° C. (1 bar), especially at 20° C. (1 bar). Further, oxygenated compounds, e.g. methanol, dimethylether, may be present.


The gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, preferably comprises less than 10 volume %, more preferably less than 5 volume %, of hydrocarbons having 6 or more carbon atoms. More preferably the gas mixture comprises less than 10 volume %, more preferably less than 5 volume %, of hydrocarbons having 5 or more carbon atoms. Even more preferably the gas mixture comprises less than 10 volume %, more preferably less than 5 volume %, of hydrocarbons having 4 or more carbon atoms. In one embodiment hydrocarbons having 3 or more carbon atoms are removed from a Fischer-Tropsch off-gas, for example using a scrubber, before it is subjected to the method of the present invention. The gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, may comprise ethane. In a preferred embodiment the amount of ethane is less than 5 wt %, more preferably less than 2 wt %, and even more preferably less than 1 wt %, calculated on the total weight of the gas mixture.
The feed rate to step (1) may, for example be about 5000 to 20000 kmoles/hr.
For steps (1) to (8), the column comprising an adsorbent bed may be made of metal, preferably stainless steel. The adsorbent bed for steps (1) to (8) comprises alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof. Preferably the adsorbent bed comprises activated carbon and/or zeolite. In another preferred embodiment the adsorbent bed comprises activated carbon and/or silicalite. When alumina is used, it is preferably combined with a carbon molecular sieve, activated carbon silicalite and/or zeolite. If zeolite is used, it may for example be ZSM-5A and/or ZSM-13 X. If silicalite is used, preferably a silicalite with a high silica to alumina molar ratio (SAR) is used. Activated carbon, silicalite and zeolite hardly adsorb nitrogen and hydrogen, but do adsorb carbon monoxide, methane, and carbon dioxide. Activated carbon, silicalite and zeolite are preferential adsorbents for methane and carbon dioxide as compared to carbon monoxide.
The absorbent bed and column are already pre-saturated and pre-pressurized with hydrogen or with a mixture of hydrogen and nitrogen upon commencement of feeding the gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen in step (1). The bed and column may be saturated and pressurized with pure hydrogen. Pure hydrogen comprises more than 90 volume %, preferably more than 95 vol %, and more preferably more than 99.9 vol % of hydrogen. The bed and column may be saturated and pressurized with a mixture of hydrogen and nitrogen. The mixture of hydrogen and nitrogen preferably comprises hydrogen in a range of between 60 to 95 vol %, and nitrogen in a range of between 5 to 40 vol %. The mixture of hydrogen and nitrogen preferably comprises less than 10 vol %, more preferably less than 5 vol %, even more preferably less than 1 vol % of gasses other than hydrogen and nitrogen. For example, the bed and column may be saturated and pressurized with a product hydrogen and nitrogen comprising gas from step (1) of an earlier cycle.
In step (1), the gas mixture is fed to one end of the adsorbent bed, and effluent is discharged from the other end of the adsorbent bed. The adsorbent bed will adsorb methane, carbon dioxide, nitrogen and carbon monoxide. The effluent will mainly comprise hydrogen and nitrogen. A part of this effluent can be used to pressurize a column and absorbent bed at the start of a cycle or in step (8). Another part of this effluent can be used in rinsing step (7). Another part can be sent as feed to a Fischer-Tropsch reaction, even though it comprises nitrogen. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 10 to 80 bar absolute (bar a), preferably 20 to 70 bar a.
In step (1), the feeding of the gas mixture and the discharging of the effluent are continued until a carbon monoxide comprising gas has reached at least 45% of the length of the bed, preferably at least 50%, more preferably at least 60%, and has reached at most 80% of the length of the bed, preferably at most 70%, calculated from the end of the bed at which the gas mixture is being fed. In a preferred embodiment, the feeding and discharging is ceased when the adsorption capacity of the adsorbent bed towards carbon monoxide is reduced by 50% to 90%, preferably 50% to 80%, more preferably 60% to 70% from its adsorption capacity towards carbon monoxide when commencing the feeding of the gas mixture.
The progress of a carbon monoxide comprising gas through the bed can be monitored. This may, for example, be performed by analyzing gas samples of the effluent and/or gas samples from the column and adsorbent bed. The progress of a carbon monoxide comprising gas through the bed may additionally or alternatively be monitored by determining the temperature along the length of the bed, e.g. by using thermocouples placed along the length of the bed. At the front of the carbon monoxide comprising gas the temperature is increased as compared to the part of the bed that has not yet been reached by the carbon monoxide comprising gas. At the front of the carbon monoxide comprising gas the temperature is also increased as compared to the part of the bed where the carbon monoxide has already been adsorbed in the adsorbent bed.
In step (2), ceasing the feeding of the gas mixture, which comprises 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, is performed by stopping the flow of gas to the column comprising an adsorbent bed. When the feeding and discharging is stopped, some hydrogen and nitrogen will remain in the column containing an adsorbent bed. Upon ceasing the feeding of the gas mixture, the pressure in the column and adsorbent bed is reduced by about 5 to 10 bar a. The pressure reduction in the column and adsorbent bed suffices to let most of the effluent, which comprises hydrogen and nitrogen, leave. The effluent leaves the column and bed at the same end from which effluent was discharged in step (1).
In optional step (3), a gas comprising at least 95 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In optional step (3) preferably a gas comprising at least 99 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In optional step (3), the gas is fed to the same end of the bed at which a gas mixture, for example Fischer-Tropsch off-gas, was fed in step (1).
The gas comprising at least 95 vol % carbon dioxide may be obtained from a place where carbon dioxide is stored, for example a carbon capture and storage (CCS) site. Additionally or alternatively, the gas comprising at least 95 vol % carbon dioxide fed to the column in step (3) may be all or a part of the effluent of step (6) of an earlier cycle. In that case the effluent of step (6) may be pressurized before it is used as feeding gas in step (3).
In step (3), effluent is discharged from the other end of the adsorbent bed. The adsorbent bed will adsorb even more carbon dioxide while a carbon dioxide comprising gas is fed. The effluent will comprise carbon monoxide. Preferably the effluent comprises at least 50 vol %, preferably at least 80 vol %, more preferably at least 90 vol %, even more preferably at least 95 vol %, still more preferably at least 99 vol % carbon monoxide, calculated on the total volume of the effluent. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 5 to 75 bar absolute (bar a), preferably 25 to 65 bar a, more preferably 30 to 55 bar a. The carbon monoxide product stream can be used as feed for a Fischer-Tropsch reaction. It can, for example, be a recycle stream in a Fischer-Tropsch process. This is very advantageous as it makes it possible to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons.
In one embodiment of the method of the present invention, an optionally scrubbed Fischer-Tropsch off-gas is used in step (1), and at least a part of the effluent of step (3) is sent as a recycle stream to the Fischer-Tropsch reactor that produced the off-gas.
In another embodiment, an optionally scrubbed Fischer-Tropsch off-gas from a first Fischer-Tropsch reactor is used in step (1), and at least a part of the effluent of step (3) is sent as a feed stream to a second Fischer-Tropsch reactor.
In a further embodiment at least a part of the effluent of step (3) is sent as a recycle stream to the Fischer-Tropsch reactor that produced the off-gas, and at least a part of the effluent of step (3) is sent as a feed stream to a second Fischer-Tropsch reactor.
In optional step (3), the feeding of a carbon dioxide comprising gas, and the discharging of the effluent are continued until at least 60%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, still more preferably at least 95% of the carbon monoxide that was present in the adsorbent bed at the commencement of this rinsing step is discharged from the other end of the bed. The carbon dioxide in the feed will replace carbon monoxide in the adsorbent bed. In one embodiment, carbon dioxide is fed in step (3) and the feeding and discharging is ceased when a breakthrough of methane is imminent.
The progress of a methane comprising gas through the bed can be monitored, e.g. by analyzing gas samples of the effluent and/or gas samples from the column and adsorbent bed. The progress of a methane comprising gas through the bed may additionally or alternatively be monitored by determining the temperature along the length of the bed, e.g. by using thermocouples placed along the length of the bed. At the front of the methane comprising gas the temperature is increased as compared to the part of the bed that has not yet been reached by the methane comprising gas. At the front of the methane comprising gas the temperature is also increased as compared to the part of the bed where the carbon dioxide has replaced the carbon monoxide and subsequently the methane in the adsorbent bed.
In step (4), a gas comprising at least 95 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In step (4) preferably a gas comprising at least 99 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In step (4), the gas is fed to the same end of the bed at which a gas mixture was fed in step (1).
Preferably the gas comprising at least 95 vol % carbon dioxide fed to the column in step (4) has a high pressure, more preferably it has a pressure in the range of between 60 and 100 bar. Preferably the gas comprising at least 95 vol % carbon dioxide is obtained from a place where carbon dioxide is stored, for example a carbon capture and storage (CCS) site.
In step (5), a gas comprising at least 95 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In step (5) preferably a gas comprising at least 99 vol % carbon dioxide is fed to the column comprising an adsorbent bed. In step (5), the gas is fed to the same end of the bed at which a gas mixture was fed in step (1).
Preferably the gas comprising at least 95 vol % carbon dioxide fed to the column in step (5) has a high pressure, more preferably it has a pressure in the range of between 60 and 100 bar. Preferably the gas comprising at least 95 vol % carbon dioxide which is fed to the column is obtained from a place where carbon dioxide is stored, for example a carbon capture and storage (CCS) site.
In step (5), effluent is discharged from the other end of the adsorbent bed. The adsorbent bed will adsorb even more carbon dioxide. The effluent will comprise methane and carbon dioxide. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 30 to 80 bar absolute (bar a), preferably 30 to 70 bar a. A product stream comprising methane and carbon dioxide is obtained. In case optional step (3) is not performed, the product stream will comprise carbon monoxide, methane and carbon dioxide.
The gas comprising methane and carbon dioxide, and optionally carbon monoxide, discharged in step (5), can be obtained at high pressure. When the gas comprising methane and carbon dioxide is recovered at a high pressure it can be fed to a gasifier or a reformer, for example an auto thermal reformer, without performing a pressurization step. The process of the present invention makes it possible to convert most of the carbon atoms of the hydrocarbonaceous feed stock to the desired C5+ hydrocarbons.
The effluent discharged in step (5) may be fed to a gasifier. The gasification may be carried out by partially oxidating, for example according to the shell gasification process (SGP) by partial oxidation using pure oxygen. The partial oxidation using pure oxygen may be operated at 1100 to 1700° C. Preferably the partial oxidation using pure oxygen is operated at 1300 to 1500° C. and pressures up to 70 bar. The gasification may be carried out by partial oxidation as described in WO9603345A1 using a co-annular burner using 99.5% pure oxygen and optionally carbon dioxide as moderator gas and in the absence of a catalyst. A further example is described in WO2008006787A2. In the process of WO2008006787A2 partial oxidation on a methane comprising feed is performed using a multi-orifice burner provided with an arrangement of separate passages, wherein the gaseous hydrocarbon having at elevated temperature flows through a passage of the burner, an oxidiser gas flows through a separate passage of the burner and wherein the passage for gaseous hydrocarbon feed and the passage for oxidiser gas are separated by a passage through which a secondary gas flows, wherein the secondary gas comprises hydrogen, carbon monoxide and/or a hydrocarbon.
The effluent discharged in step (5) may be fed to a reformer. The reforming may be carried out using a reforming process, preferably using a steam reforming process. More preferably a steam methane reforming process (SMR), an adiabatic steam reforming process (ASR), a fired steam reforming process, or an auto thermal steam reforming process (ATR) is used. Most preferably an auto thermal steam reforming process (ATR) is used. Even more preferably an ATR process is used in which gas heated reforming (GHR) is incorporated. The ATR and the GHR can be linked in different ways; the configuration in which feed gas passes through the GHR and ATR in series is preferred. Hence, the effluent discharged in step (5) most preferably is fed to an ATR, even more preferably to a GHR and ATR which are placed in series.
In step (5), the feeding of carbon dioxide and the discharging of the effluent are continued until at least 60%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, still more preferably at least 95% of the methane that was present in the adsorbent bed at the commencement of this rinsing step is discharged from the other end of the bed. Carbon dioxide in the feed will replace methane in the adsorbent bed.
The progress of a carbon dioxide comprising gas through the bed can be monitored, e.g. by analyzing gas samples of the effluent and/or gas samples from the column and adsorbent bed. The progress of a carbon dioxide comprising gas through the bed may additionally or alternatively be monitored by determining the temperature along the length of the bed, e.g. by using thermocouples placed along the length of the bed. At the front of the carbon dioxide comprising gas the temperature is increased as compared to the part of the bed that has not yet been reached by the carbon dioxide comprising gas. At the front of the carbon dioxide comprising gas the temperature is also increased as compared to the part of the bed where the carbon dioxide has already replaced methane in the adsorbent bed.
Preferably the feeding and said discharging are continued in step (5) is until an amount of carbon dioxide equal to at least 50%, preferably at least 60%, more preferably 50 to 80%, even more preferably 60 to 80%, of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed. The aim of this is to recover the same or a similar amount of carbon dioxide as was present in the gas fed to step (1), which preferably is Fischer-Tropsch off-gas.
It is thus the amount of discharged carbon dioxide which is aimed for in step (5). Although it may take place, the aim is not to displace carbon dioxide molecules in the bed with carbon dioxide molecules from the gas that is fed to the column in step (5). The discharged carbon dioxide may partly or completely be carbon dioxide that is fed to the column in step (5) and which is then discharged at the other end of the column.
The velocity of the feed may be relatively low. The feed rate to step (5) may, for example be about 5000 to 10000 kmoles/hr.
One way to control the amount of carbon dioxide in the effluent in step (5) is to determine the amount of carbon dioxide in the gas fed to step (1) and to determine the amount of carbon dioxide that is discharged in step (5). The feeding and said discharging are continued in step (5) is until an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed.
Another way to control the amount of carbon dioxide in the effluent of step (5) is to control the feed ratios to steps (1) and (5). When the composition and the feed rate of step (1) are known, and the composition and the feed rate of step (5) are known, one can calculate the amount of carbon dioxide that is discharged in step (5) as compared to the amount of carbon dioxide in the gas fed to step (1). Preferably the ratio between the flow rate of the gas fed to step (1) and the flow rate of the gas fed to step (5) is in the range of between 0.1 to 2, preferably 0.5 to 2, more preferably 0.8 to 1.2. The feed rate to step (1) may, for example be about 5000 to 20000 kmoles/hr. This way of controlling the amount of carbon dioxide in the effluent of step (5) is especially suitable when repeated cycles of steps (1) to (8) are performed. This way of controlling the amount of carbon dioxide in the effluent of step (5) is even more suitable when repeated cycles of steps (1) to (8) are performed in several columns which are connected in parallel. When repeated cycles of steps (1) to (8) are performed, per cycle the feeding and said discharging are preferably continued in step (5) until an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed.
In step (6), the feeding of a gas comprising at least 95 vol % carbon dioxide is ceased. The pressure of the column and adsorbent bed is reduced to a pressure in the range of 1 to 5 bar a. During step (6) carbon dioxide leaves the column and bed at the same end at which in step (5) carbon dioxide was fed to the column and bed. All or a part of this effluent may be fed to a carbon capture and storage (CCS) site. The gas needs to be pressurized before it is stored in a CCS site. A part of this carbon dioxide may be used as feed for step (3).
In step (6) the pressure may be reduced in two stages. For example, the effluent obtained in the first stage may be fed to step (3), and the effluent obtained in the second stage may, after pressurization, be stored in a CCS site.
In step (7), the column and adsorbent bed are rinsed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed. The mixture of hydrogen and nitrogen is fed to the same end of the column and bed from which effluent was discharged in step (1). During step (7) residual carbon dioxide leaves the column and bed at the same end at which in step (1) a gas mixture was fed to the column and bed.
In a preferred embodiment, the mixture of hydrogen and nitrogen used in step (7) is a part of the effluent from step (2), and may optionally also comprise a part of the effluent from step (1).
In a preferred embodiment, the mixture of hydrogen and nitrogen used in step (7) is a part of the effluent from step (D) and/or step (E).
In a preferred embodiment, the mixture of hydrogen and nitrogen used in step (7) is a part of the effluent from step (2) and a part of the effluent from step (D) and/or step (E). It may optionally also comprise a part of the effluent from step (1).
The gas mixture fed to the column and bed rinses the bed from carbon dioxide. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 1 to 5 bar a. The effluent can be sent to a fuel pool.
In a preferred embodiment, the column and adsorbent bed are rinsed in step (7) by feeding a gas comprising at least 95 vol % nitrogen, preferably at least 99 vol % nitrogen, through the column and adsorbent bed, followed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed, whereby the column and bed are at a pressure in the range of 1 to 5 bar a. The gas comprising at least 95 vol % nitrogen, preferably at least 99 vol % nitrogen, may be the product of an air separation unit (ASU). The mixture of hydrogen and nitrogen preferably is a part of the effluent from step (2) and/or steps (D) and (E), and may optionally also comprise a part of the effluent from step (1). The gas comprising at least 95 vol % nitrogen, and in a subsequent step the mixture of hydrogen and nitrogen, are fed to the same end of the column and bed from which effluent was discharged in step (1). When the gas comprising at least 95 vol % nitrogen is fed to the column and bed, a part of the residual carbon dioxide leaves the column and bed at the same end at which in step (1) a gas mixture was fed to the column and bed. This effluent can be sent to a fuel pool.
In step (8) the column and adsorbent bed are pressurized to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a mixture of hydrogen and nitrogen. The mixture used may comprise a part of the product hydrogen and nitrogen from step (1), and may optionally also comprise a part of the product hydrogen and nitrogen from step (2). The mixture of hydrogen and nitrogen preferably comprises hydrogen in a range of between 60 to 95 vol %, and nitrogen in a range of between 5 to 40 vol %. The mixture of hydrogen and nitrogen preferably comprises less than 10 vol %, more preferably less than 5 vol %, even more preferably less than 1 vol % of gases other than hydrogen and nitrogen.
In a preferred embodiment, steps (A) to (G) are performed. In this preferred embodiment, a gas comprising at least 80 vol % hydrogen, calculated on the total volume of this hydrogen comprising gas, is produced. The gas preferably comprising at least 80 vol % hydrogen is obtained in steps (A), (B), and (C).
The gas comprising at least 80 vol % hydrogen may be recycled to a Fischer-Tropsch reactor.
As described above, steps (1) to (8) may be performed using a single column comprising an adsorbent bed. As described above, preferably repeated cycles of steps (1) to (8) are performed. Preferably at least two, preferably at least six, columns that comprise an adsorbent bed are used for steps (1) to (8). Preferably the columns for steps (1) to (8) are connected in parallel.
In a preferred embodiment of the present invention repeated cycles of steps (A) to (G) are performed. Effluent from one step can be used as feeding gas in another step; this is especially advantageous when repeated cycles of steps (A) to (G) are performed.
Steps (A) to (G) may be performed using a single column comprising an adsorbent bed. Preferably several columns that comprise an adsorbent bed are used. When using more than one column, the columns are preferably connected in parallel. Preferably the repeated cycles of steps (A) to (G) are performed over each column. In a preferred embodiment at least one column is subjected to one step of the cycle while another column is subjected to another step of the cycle. The product of one column can be used in another column, for example for purge, pressurization or rinse. In one embodiment at least two columns comprising an adsorbent bed, preferably at least five columns comprising an adsorbent bed, are subjected to repeated cycles of steps (A) to (G). Preferably at most 20, more preferably at most 15, columns comprising an adsorbent bed are subjected to repeated cycles of steps (A) to (G).
Preferably at least two, preferably at least six, columns that comprise an adsorbent bed are used for steps (1) to (8) and at least two, preferably at least five, columns that comprise an adsorbent bed are used for steps (A) to (G).
Preferably one column or one set of columns is used for steps (1) to (8) and another column or another set of columns is used for steps (A) to (G).
Preferably the columns for steps (1) to (9) are connected in parallel, and the columns for steps (A) to (G) are connected in parallel.
In case steps (1) to (8) and steps (A) to (G) are performed, preferably use is made of two different pressure swing adsorption units (PSA units); one PSA for steps (1) to (8), and one PSA for steps (A) to (G).
The feed gas for step (A) is at least a part of the effluent of step (1).
The feed gas for step (A) preferably comprises 10 to 40 volume % nitrogen and 60 to 90 volume % hydrogen. More preferably the feed gas for step (A) comprises 15 to 35 volume % nitrogen and 65 to 85 volume % hydrogen.
For steps (A) to (G), the column comprising an adsorbent bed may be made of metal, preferably stainless steel. The adsorbent bed for steps (A) to (G) comprises alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof. Preferably the adsorbent bed comprises a zeolite. When alumina is used, it is combined with a zeolite. The zeolite may for example be ZSM-5A and/or ZSM-13 X and/or a LiX zeolite. Zeolite is a preferential adsorber for nitrogen as compared to hydrogen.
The absorbent bed and column are already pre-saturated and pre-pressurized with hydrogen upon commencement of feeding the effluent of step (1) in step (A). The bed and column may be saturated and pressurized with pure hydrogen. Pure hydrogen comprises more than 90 volume %, preferably more than 95 vol %, and more preferably more than 99.9 vol % of hydrogen. The bed and column may be saturated and pressurized with a product hydrogen comprising gas from step (A) of an earlier cycle.
In step (A), effluent is discharged from the other end of the adsorbent bed. The adsorbent bed will adsorb nitrogen. The effluent will mainly comprise hydrogen. A part of this effluent can be used to pressurize a column and absorbent bed at the start of a cycle or in step (G). Another part can be sent as feed to a Fischer-Tropsch reaction. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 20 to 80 bar absolute (bar a), preferably 30 to 70 bar a.
In step (A), the feeding of the gas mixture and the discharging of the effluent are continued until a front of nitrogen comprising gas has reached at least 45% of the length of the bed, preferably at least 50%, more preferably at least 60%, and has reached at most 80% of the length of the bed, preferably at most 70%, calculated from the end of the bed at which the gas mixture is being fed. In a preferred embodiment, the feeding and discharging is ceased when the adsorption capacity of the adsorbent bed towards nitrogen is reduced by 50% to 80%, preferably 60% to 70% from its adsorption capacity towards nitrogen when commencing the feeding of the gas mixture. The progress of a nitrogen comprising gas through the bed can be monitored, e.g. by analyzing gas samples of the effluent and/or gas samples from the column and adsorbent bed. The progress of a nitrogen comprising gas through the bed may additionally or alternatively be monitored by determining the temperature along the length of the bed, e.g. by using thermocouples placed along the length of the bed. At the front of the nitrogen comprising gas the temperature is increased as compared to the part of the bed that has not yet been reached by the nitrogen comprising gas. At the front of the nitrogen comprising gas the temperature is also increased as compared to the part of the bed where nitrogen has already been adsorbed.
In step (B), ceasing the feeding of the gas mixture is performed by stopping the flow of gas to the column comprising an adsorbent bed. When the feeding and discharging is stopped, some hydrogen and nitrogen will remain in the column containing an adsorbent bed. Upon ceasing the feeding of the gas mixture, the pressure in the column and adsorbent bed is preferably reduced by in total about 5 to 10 bar a in steps (B) and (C). Most preferably steps (B) and (C) are performed as separate steps. It is also possible to combine steps (B) and (C) and reduce the pressure in the column and absorbent bed by in total about 5 to 10 bar a in a single step. When steps (B) and (C) are preformed separately, the pressure in the column and bed is reduced in step (B) by about 2 to 5 bar a, and is further reduced in step (C) by another 2 to 5 bar a. The pressure reduction in the column and adsorbent bed suffices to let most of the effluent, which comprises hydrogen, leave. During steps (B) and (C) the effluent leaves the column and bed at the same end from which effluent was discharged in step (A).
In step (D), the pressure of the column and adsorbent bed is reduced to a pressure in the range of 1 to 5 bar a. During step (D) hydrogen and nitrogen leave the column and bed at the same end at which in step (A) effluent of step (1) was fed to the column and bed. The effluent can be sent to a fuel pool. During step (D) almost all hydrogen and nitrogen leave the column and bed. Additionally or alternatively at least a part of the effluent of step (D) can be used as a feeding gas in step (7).
In step (E), the column and adsorbent bed are rinsed by feeding hydrogen through the column and adsorbent bed. The hydrogen is fed to the same end of the column and bed from which effluent was discharged in step (A). During step (E) residual nitrogen leaves the column and bed at the same end at which in step (A) an effluent from step (1) was fed to the column and bed.
In a preferred embodiment, the hydrogen used in step (E) is a part of the effluent from step (C), and may optionally also comprise a part of the effluent from step (B) and/or (A).
Optionally, in step (E) the column is first rinsed with effluent from step (C) before it is rinsed by feeding a gas comprising more than 95 volume % hydrogen, preferably a gas comprising 90 to 99.9 volume % hydrogen, through the column and adsorbent bed.
The hydrogen fed to the column and bed rinses the bed from nitrogen. The pressure of the effluent gas will be about the same as the pressure in the column and the adsorbent bed and will thus be in the range of 1 to 5 bar a. The effluent can be sent to a fuel pool. Additionally or alternatively at least a part of the effluent of step (E) can be used as a feeding gas in step (7).
In steps (F) and (G) the column and adsorbent bed are pressurized to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding hydrogen. In step (F), the hydrogen used may be or may comprise a part of the product hydrogen from step (B), and may optionally also comprise a part of the product hydrogen from step (A). In step (G), the hydrogen preferably is a part of the product hydrogen from step (A). Most preferably steps (F) and (G) are performed as separate steps. When steps (F) and (G) are preformed separately, the column and bed are pressurized in step (F) to a pressure in the range of 5 to 50 bar a, preferably 10 to 45 bar a, more preferably 20 to 40 bar a, and is further pressurized in step (G) to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a. It is also possible to combine steps (F) and (G) and pressurize the column and absorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding hydrogen in a single step using hydrogen from step (A) and optionally also hydrogen from step (B).
The hydrogen fed to the column in steps (E), (F) and (G) preferably is pure hydrogen. The hydrogen fed to the column in steps (E), (F) and (G) preferably is a gas comprising more than 95 volume % hydrogen, more preferably a gas comprising 90 to 99.9 volume % hydrogen. Rinsing step (E) may be performed with product hydrogen comprising gas of steps (A), (B) and/or (C).
In a another preferred embodiment, the invention provides a method for recovering carbon monoxide and carbon dioxide from a gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, said method comprising, in sequence, the following steps:

    (1) feeding a gas mixture through a column comprising an adsorbent bed,
    
        said gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture,
        the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
        with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 10 to 80 bar absolute (bar a), preferably 20 to 70 bar a, with pure hydrogen, or with a mixture of hydrogen and nitrogen, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until a carbon monoxide comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and
    
    
    (2) ceasing the feeding of the gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, and reducing the pressure in the column and the bed by about 5 to 25 bar a, preferably by 10-25 bar a, more preferably by 15-20 bar a; and
    (3) rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 5 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until at least 60% of the carbon monoxide that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed;
    
    
    (4) pressurizing the column and adsorbent bed by about 5 to 25 bar a by feeding a gas comprising at least 95 vol % carbon dioxide,
    (5) rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide, through the column and adsorbent bed,
    
        the column and bed being at a pressure in the range of 30 to 80 bar a, preferably 30 to 70 bar a, and
        discharging effluent from the other end of said bed, and
        continuing said feeding and said discharging until
        
            at least 60% of the methane that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed, and
            optionally an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed; and
        
        
    
    
    (6) ceasing the feeding of a gas comprising at least 95 vol % carbon dioxide, and reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
    (7) rinsing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed
    
        the column and bed being at a pressure in the range of 1 to 5 bar a, and
    
    
    (8) pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a, preferably 25 to 65 bar a, more preferably 30 to 55 bar a by feeding a mixture of hydrogen and nitrogen,

said method further comprising, in sequence, the following steps:

    (I) sending at least a part of the discharged effluent of step (1) as feed to a membrane unit,
    (II) optionally sending at least a part of the discharged effluent of step (3) as sweep gas to the membrane unit,
    (III) optionally sending at least a part of the retentate of the membrane unit as feed to step (7),
    (IV) sending at least a part of the permeate of the membrane unit as feed to a Fischer-Tropsch reaction.


In this preferred embodiment of the present invention a gas stream comprising hydrogen and carbon monoxide is produced which may be used as feed for a Fischer-Tropsch reaction. The produced gas comprising at least 80% carbon monoxide, which is effluent of step (3), may be partly or completely used to produce the gas stream comprising hydrogen and carbon monoxide.
In a preferred embodiment steps (II) and (III) are performed.
Steps (I) to (IV) and steps (A) to (G) as described above preferably are not combined. The process of the present invention preferably has either additional steps (A) to (G) or additional steps (I) to (IV).
The membrane unit that can be used can comprise a polymeric membrane or a ceramic membrane, preferably a polymeric membrane, most preferably a polyimide membrane. Such membranes are commercially available.
Discharged effluent of step (1) comprises nitrogen and hydrogen and is sent as feed to a membrane unit. Also a sweep gas is sent to the membrane unit. The sweep gas preferably comprises carbon monoxide and may be discharged effluent of step (3).
In the membrane unit, feed comprising nitrogen and hydrogen is sent to one side of the membrane and sweep gas comprising carbon monoxide is sent to the other side of the membrane. The feed comprising nitrogen and hydrogen which is sent as feed to one side of the membrane preferably is at a higher pressure as compared to the sweep gas comprising carbon monoxide which is sent to the other side of the membrane. The feed may, for example, be at a pressure in the range of from 30 to 70 bar a.
In the membrane unit, hydrogen flows through the membrane. Preferably nitrogen and carbon monoxide do not or hardly flow through the membrane. Hydrogen present in the feed to the membrane unit becomes part of the permeate. The permeate of the membrane unit comprises carbon monoxide and hydrogen. Permeate may be sent as feed to a Fischer-Tropsch reaction. The retentate of the membrane unit comprises nitrogen. Retentate may be sent as feed to step (7).
Some embodiments of the method according to the invention will be illustrated below with reference to the attached figures. It is noted that the present invention should not be considered limited thereto or thereby.
FIG. 1 illustrates an overview of the process steps of a preferred method according to the invention. One column comprising an adsorbent bed is depicted eight times; each time it shows a step of steps (1) to (8) according to the invention. Another column comprising an adsorbent bed is depicted seven times; each time it shows a step of steps (A) to (G) according to the invention. In step (1) Fischer-Tropsch off-gas is fed to the column and bed and a mixture of hydrogen and nitrogen is discharged. During step (1) the pressure in the column and bed is high. In step (2) the pressure is reduced by 5 to 10 bar a, and a remainder of hydrogen and nitrogen is discharged. In step (3) the column and bed are rinsed by feeding them with carbon dioxide and discharging carbon monoxide. The carbon monoxide stream can be sent as feed to a Fischer-Tropsch reaction. In step (4) the column and bed are pressurized by feeding with carbon dioxide at high pressure. In step (5) the column and bed are rinsed by feeding them with carbon dioxide and discharging a mixture of methane and carbon dioxide. The mixture of methane and carbon dioxide is obtained as a product stream and is at a high pressure. This product may be fed to a gasifier or a reformer, for example an auto thermal reformer, without performing a pressurization step. In step (6) the pressure in the column and bed is reduced to 1 to 5 bar a, and carbon dioxide is discharged. A part of this carbon dioxide may be sent to CCS. The gas needs to be pressurized before it is stored in a CCS site. A part of this carbon dioxide may be used as feed for step (3). In step (7) a mixture of hydrogen and nitrogen is fed to the column and bed and the effluent may be sent to the fuel pool. In step (8) the column and bed are pressurized to a high pressure again using a mixture of hydrogen and nitrogen. During step (A) the pressure in the column and bed is high. In steps (B) and (C) the pressure is reduced in total by 5 to 10 bar a, and a remainder of hydrogen is discharged. In step (D) the pressure in the column and bed is reduced to 1 to 5 bar a, and hydrogen and nitrogen are discharged. In step (E) hydrogen is fed to the column and bed and the effluent may be sent to the fuel pool. In steps (F) and (G) the column and bed are pressurized to a high pressure again using hydrogen.
FIG. 2 shows an overview of the process steps of another embodiment of the method of the present invention. In this embodiment the optional rinsing step is not performed. One column comprising an adsorbent bed is depicted seven times; each time it shows a step of steps (1) to (7) according to the invention. Another column comprising an adsorbent bed is depicted seven times; each time it shows a step of steps (A) to (G) according to the invention. In step (1) Fischer-Tropsch off-gas is fed to the column and bed and a mixture of hydrogen and nitrogen is discharged. During step (1) the pressure in the column and bed is high. In step (2) the pressure is reduced by 5 to 10 bar a, and a remainder of hydrogen and nitrogen is discharged. In step (3) the column and bed are pressurized by feeding with carbon dioxide at high pressure. In step (4) the column and bed are rinsed by feeding them with carbon dioxide and discharging a mixture of methane, carbon monoxide and carbon dioxide. The mixture of methane, carbon monoxide and carbon dioxide is obtained as a product stream and is at a high pressure. This product may be fed to a gasifier or a reformer, for example an auto thermal reformer, without performing a pressurization step. In step (5) the pressure in the column and bed is reduced to 1 to 5 bar a, and carbon dioxide is discharged. A part of this carbon dioxide may be sent to CCS. The gas needs to be pressurized before it is stored in a CCS site. A part of this carbon dioxide may be used as feed for step (3). In step (6) a mixture of hydrogen and nitrogen is fed to the column and bed and the effluent may be sent to the fuel pool. In step (7) the column and bed are pressurized to a high pressure again using a mixture of hydrogen and nitrogen. During step (A) the pressure in the column and bed is high. In steps (B) and (C) the pressure is reduced in total by 5 to 10 bar a, and a remainder of hydrogen is discharged. In step (D) the pressure in the column and bed is reduced to 1 to 5 bar a, and hydrogen and nitrogen are discharged. In step (E) hydrogen is fed to the column and bed and the effluent may be sent to the fuel pool. In steps (F) and (G) the column and bed are pressurized to a high pressure again using hydrogen.
While the method has been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the disclosure need not be limited to the disclosed embodiments. It is intended to cover various modifications, combinations and similar arrangements included within the spirit and scope of the claims, the scope of which should be accorded the broadest interpretation so as to encompass all such modifications and similar structures. The present disclosure includes any and all embodiments of the following claims.
It should also be understood that a variety of changes may be made without departing from the essence of the invention. Such changes are also implicitly included in the description. They still fall within the scope of this invention. It should be understood that this disclosure is intended to yield a patent covering numerous aspects of the invention both independently and as an overall system and in both method and apparatus modes.
Any patents, publications, or other references mentioned in this application for patent are hereby incorporated by reference. In addition, as to each term used, it should be understood that unless its utilization in this application is inconsistent with such interpretation, common dictionary definitions should be understood as incorporated for each term and all definitions, alternative terms, and synonyms such as contained in at least one of a standard technical dictionary recognized by artisans.

## Claims

1. A method for recovering carbon monoxide and carbon dioxide from a gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, said method comprising, in sequence, the following steps:
(1) feeding a gas mixture through a column comprising an adsorbent bed, said gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, calculated on the total volume of the gas mixture, the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 10 to 80 bar absolute (bar a), with pure hydrogen, or with a mixture of hydrogen and nitrogen, and
discharging effluent from the other end of said bed, and
continuing said feeding and said discharging until a carbon monoxide comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and

(2) ceasing the feeding of the gas mixture comprising 5-50 vol % methane, 10-50 vol % carbon dioxide, 20-65 vol % carbon monoxide, 10-40 vol % hydrogen and 10-55 vol % nitrogen, and reducing the pressure in the column and the bed by about 5 to 25 bar a, and
(3) optionally rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide through the column and adsorbent bed,
the column and bed being at a pressure in the range of 5 to 75 bar a, and
discharging effluent from the other end of said bed, and
continuing said feeding and said discharging until at least 60% of the carbon monoxide that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed;

(4) pressurizing the column and adsorbent bed by about 5 to 25 bar a by feeding a gas comprising at least 95 vol % carbon dioxide,
(5) rinsing the column and the adsorbent bed by feeding a gas comprising at least 95 vol % carbon dioxide, through the column and adsorbent bed,
the column and bed being at a pressure in the range of 30 to 80 bar a, and
discharging effluent from the other end of said bed, and
continuing said feeding and said discharging until
at least 60% of the methane that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed, and

(6) ceasing the feeding of a gas comprising at least 95 vol % carbon dioxide, and reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
(7) rinsing the column and adsorbent bed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed
the column and bed being at a pressure in the range of 1 to 5 bar a, and

(8) pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a by feeding a mixture of hydrogen and nitrogen.

2. A method according to claim 1, wherein the feeding and discharging of step (5) are continued until
at least 60% of the methane that was present in the bed at the commencement of this rinsing step is discharged from the other end of said bed, and
an amount of carbon dioxide equal to at least 50% of the amount of carbon dioxide that was present at the commencement of this rinsing step is discharged from the other end of said bed.

3. A method according to claim 1, wherein step (3) is performed.

4. A method according to claim 1, wherein repeated cycles of steps (1) to (8) are performed.

5. A method according to claim 1, wherein at least two columns that comprise an adsorbent bed are used for steps (1) to (8).

6. A method according to claim 5, wherein the columns for steps (1) to (8) are connected in parallel.

7. A method according to claim 1, wherein at least a part of the discharged effluent of step (3) is sent as feed to a Fischer-Tropsch reaction.

8. A method according to claim 1, wherein the column and adsorbent bed are rinsed in step (7)
by feeding a gas comprising at least 95 vol % nitrogen through the column and adsorbent bed,
followed by feeding a mixture of hydrogen and nitrogen through the column and adsorbent bed,
the column and bed being at a pressure in the range of 1 to 5 bar a.

9. A method according to claim 1, wherein a part of the effluent of step (2) is used as feeding gas in step (7).

10. A method according to claim 9, wherein additionally a part of the effluent of step (1) is used as feeding gas in step (7).

11. A method according to claim 1, wherein a part of the effluent of step (1) is used as feeding gas in step (8).

12. A method according to claim 11, wherein additionally a part of the effluent of step (2) is used as feeding gas in step (8).

13. A method according to claim 1, wherein a scrubbed Fischer-Tropsch off-gas from a Fischer-Tropsch reactor is fed to the column and adsorbent bed in step (1), and a part of the effluent of step (3) is sent as a recycle stream to the Fischer-Tropsch reactor that produced the off-gas.

14. A method according to claim 1, wherein a scrubbed Fischer-Tropsch off-gas from a first Fischer-Tropsch reactor is used in step (1), and a part of the effluent of step (3) is sent as a feed stream to a second Fischer-Tropsch reactor.

15. A method according to claim 1 further comprising, in sequence, the following steps:
(A) feeding the effluent of step (1) through a column comprising an adsorbent bed, the adsorbent bed comprising alumina, a carbon molecular sieve, silicalite, activated carbon, a zeolite, or mixtures thereof,
with upon commencement of said feeding, the bed and column being pre-saturated and pre-pressurized to a pressure in the range of 20 to 80 bar absolute (bar a) with a gas comprising more than 95 volume % hydrogen, and
discharging effluent from the other end of said bed, and
continuing said feeding and said discharging until a nitrogen comprising gas has reached at least 45% of the length of the bed and has reached at most 80% of the length of the bed, calculated from the end of the bed at which the gas mixture is being fed; and

(B) ceasing the feeding of the effluent of step (1), and reducing the pressure in the column and the bed by about 2 to 5 bar a; and
(C) further reducing the pressure in the column and the bed by about 2 to 5 bar a; and
(D) reducing the pressure of the column and adsorbent bed to a pressure in the range of 1 to 5 bar a; and
(E) rinsing the column and adsorbent bed by feeding a gas comprising more than 95 volume % hydrogen through the column and adsorbent bed
the column and bed being at a pressure in the range of 1 to 5 bar a, and

(F) pressurizing the column and adsorbent bed to a pressure in the range of 5 to 50 bar a by feeding a gas comprising more than 95 volume % hydrogen and
(G) further pressurizing the column and adsorbent bed to a pressure in the range of 15 to 75 bar a by feeding a gas comprising more than 95 volume % hydrogen.

16. A method according to claim 15, wherein repeated cycles of steps (A) to (G) are performed.

17. A method according to claim 15, wherein at least two columns that comprise an adsorbent bed are used for steps (A) to (G).

18. A method according to claim 17, wherein the columns for steps (A) to (G) are connected in parallel.

19. A method according to claim 15, wherein at least a part of the discharged effluent of step (A) is sent as feed to a Fischer-Tropsch reaction.