WO2012123752A2 - Procédé et appareil pour la séparation de dioxyde de carbone et d'hydrogène - Google Patents
Procédé et appareil pour la séparation de dioxyde de carbone et d'hydrogène Download PDFInfo
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- WO2012123752A2 WO2012123752A2 PCT/GB2012/050574 GB2012050574W WO2012123752A2 WO 2012123752 A2 WO2012123752 A2 WO 2012123752A2 GB 2012050574 W GB2012050574 W GB 2012050574W WO 2012123752 A2 WO2012123752 A2 WO 2012123752A2
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- B01D53/14—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 absorption
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- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C01B2203/0465—Composition of the impurity
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- C01B2203/146—At least two purification steps in series
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Definitions
- This invention relates to processes and apparatus for the low temperature separation of carbon dioxide and hydrogen.
- CCS Carbon dioxide Capture and Storage
- EOR enhanced oil recovery techniques
- the carbon dioxide can be sequestered in the depleted reservoir for long-term storage.
- a carbon dioxide purity of 95% or higher is likely to be of economic benefit to minimise compression power, the size of transportation systems, and storage volumes.
- the carbon dioxide is usually compressed to high pressure (typically around 10,000 to 20,000 kPa, for example 15,000 kPa) for transportation and storage [as used herein the unit kPa refers to absolute pressure unless stated otherwise]. Compression of C0 2 to such high pressures is an energy intensive process, and thus power consumption is a key consideration for any CCS model.
- a conventional technique for carbon capture is "post-combustion capture".
- a potential disadvantage of conventional post-combustion capture processes is that the concentration of carbon dioxide in the flue gas is relatively low (generally around 10 to 20% on a dry basis). Since extraction of carbon dioxide from streams containing high carbon dioxide content is easier than from those with lower carbon dioxide content and equipment is physically smaller due to the feed gas flow being relatively low, pre- combustion capture and oxy-fuel combustion processes have been proposed as alternatives to conventional post-combustion capture processes. Furthermore, the efficient use of geological formations for the capture of carbon dioxide requires that the carbon dioxide sent for storage should be substantially free of other components. In particular, purer carbon dioxide is required to meet the specifications for EOR. Alternative approaches to flue gas processing for the recovery of carbon dioxide from combustion processes can facilitate the use of process technology that produces purer carbon dioxide.
- Pre-combustion capture involves the production of synthesis gas (comprising hydrogen, carbon monoxide, water and carbon dioxide) either by reforming of natural gas or by gasification of coal or biomass. Additional hydrogen can be recovered by a water-gas shift reaction with the carbon monoxide produced reacting with water to form carbon dioxide and hydrogen. Conditioned hydrogen may subsequently be burnt in a turbine, producing only water as a combustion by-product. Usually a combined cycle turbine is used in a process known as integrated gasification combined cycle (IGCC).
- IGCC integrated gasification combined cycle
- the present invention provides novel processes and apparatus for the separation of carbon dioxide and hydrogen gases.
- novel heat integration techniques are used to improve the efficiency of the process and to minimise the power requirements for downstream compression.
- the present invention provides a separation process wherein C0 2 is separated from a gaseous feed stream comprising C0 2 and H 2 , the process comprising the steps of:
- step (ii) passing the cooled and partially condensed feed stream from step (i) to a first vapour-liquid separator to produce a vapour stream having increased H 2 content relative the feed stream and a liquid stream having increased C0 2 content relative to the feed stream;
- step (iv) passing the expanded stream from step (iii) to a second vapour-liquid separator to produce a vapour stream having increased H 2 content relative the liquid stream from step (ii) and a liquid stream having increased C0 2 content relative to the liquid stream from step (ii);
- step (v) expanding and heating a first portion of the liquid stream from step (iv); wherein cooling in step (i) is provided at least in part by heat exchange during heating of the first portion of the liquid stream from step (iv) in step (v).
- the gaseous feed stream is preferably supplied to step (i) of the process of the invention at a pressure in the range of from 2000 to 10,000 kPa, more preferably from 3000 to 9000 kPa, and still more preferably from 4000 to 8000 kPa, for example 5000 kPa, 6000 kPa or 7000 kPa.
- a gaseous feed stream to be separated according to the invention will be supplied at atmospheric pressure and will be compressed to a pressure in the range of from 1000 to 10,000 kPa to form the gaseous feed stream.
- a multistage compression train may be used to form the gaseous feed stream.
- the gaseous feed stream is preferably supplied to step (i) of the process of the invention at a temperature in the range of from 0 to 50 °C, more preferably 10 to 30 °C, for example 15 °C.
- the gaseous feed stream is preferably cooled to a temperature of from -30 to -55 °C, more preferably from -40 to -55 °C, still more preferably from -45 to -55 °C, and most preferably from -50 to -55 °C for example -51 °C, -52 °C, -53 °C, or -54 °C. It will be appreciated that carbon dioxide freezes at -56.6 °C and thus -55 °C is an effective lower limit for the operating temperature in the process of the invention.
- the operating pressure of the second vapour-liquid separator is preferably in the range of from 1000 to 6000 kPa, more preferably 2000 to 5000 kPa, for example 3000 kPa or 4000 kPa. Due to the thermodynamic properties of the C0 2 rich liquid stream from step (ii), the operating temperature of the second vapour liquid separator is essentially the same as that of the first vapour-liquid separator.
- the operating temperature of the second vapour- liquid separator is preferably in the range of from -30 to -55 °C, more preferably from -40 to -55 °C, still more preferably from -45 to -55 °C, and most preferably from -50 to -55 °C, for example -51 °C, -52 °C, -53 °C, or -54 °C.
- step (i) At least a portion of the cooling duty in step (i) is provided by heat exchange with the first portion of the expanded liquid stream from step (iv). Expansion of the first portion of the liquid stream in step (iv) provides a reduced pressure stream which is evaporated in heat exchange with the gaseous feed stream. In this way, the cooling requirements in step (i) are integrated with the heating requirements in step (v).
- step (v) may lead to cooling of the stream by the Joule Thomson effect. This can potentially lead to freezing of the expanded stream.
- the first portion of the liquid stream from step (iv) may be heated to a temperature in the range of from -35 to -45 °C prior to expansion in step (v). Heating of the first portion of the liquid stream from step (iv) prior to expansion is preferably by heat exchange during cooling of the gaseous feed stream.
- the first portion of the liquid stream from step (iv) preferably comprises 50 wt% or less, more preferably 45 wt% or less, and most preferably 40 wt% or less of the liquid stream from step (iv).
- the first portion of the liquid stream from step (iv) preferably comprises 10 wt% or more, more preferably 15 wt% or more, and most preferably 20 wt% or more of the liquid stream from step (iv).
- the first portion of the liquid stream from step (iv) will generally have a pressure in the range of from 200 to 2000 kPa, more preferably 300 to 1500 kPa, still more preferably 400 to 1200 kPa, still more preferably 500 to 1000 kPa, and most preferably 600 to 800 kPa.
- the first portion of the liquid stream from step (iv) will generally have a temperature approaching that of the gaseous feed stream, from instance in the range of from -10 to 40 °C, more preferably 0 to 30 °C, for instance 5 to
- the present invention provides the advantage that the cooling provided by expansion of the first portion of the liquid stream from step (iv) can be closely matched with the cooling requirements in step (i). In this way, unnecessary expansion of the remainder of the liquid stream from step (iv) can be avoided.
- the amount of the C0 2 product stream i.e. the liquid stream from step (iv) which is expanded in step (v)
- a surprising reduction is obtained in the power requirements for downstream compression of the C0 2 product, while still providing adequate cooling to the gaseous feed stream in step (i).
- the first portion of the liquid stream from step (iv) is preferably compressed by known procedures to form a compressed C0 2 product.
- the compressed C0 2 product is suitable for sequestration or for EOR applications.
- the process of the invention further comprises the step of:
- step (vi) expanding and heating a second portion of the liquid stream from step (iv); wherein further cooling in step (i) is provided by heat exchange during heating of the second portion of the liquid stream from step (iv) in step (v).
- the second portion of the liquid stream from step (iv) preferably comprises 50 wt% or less, more preferably 45 wt% or less, and most preferably 40 wt% or less of the liquid stream from step (iv).
- the second portion of the liquid stream from step (iv) preferably comprises 10 wt% or more, more preferably 15 wt% or more, and most preferably 20 wt% or more of the liquid stream from step (iv).
- the second portion of the liquid stream from step (iv) remains at a higher pressure following expansion in step (vi) than the first portion of the liquid stream from step (iv) following expansion in step (v).
- the second portion of the liquid stream from step (iv) will generally have a pressure in the range of from 800 to 2500 kPa, more preferably from 800 to 2000 kPa, and most preferably from 1000 to 1500 kPa.
- the second portion of the liquid stream from step (iv) will generally have a temperature approaching that of the gaseous feed stream, from instance in the range of from -10 to 40 °C, more preferably 0 to 30 °C, for instance 5 to 25 °C.
- Cooling in step (i) is thus preferably provided by at least one low pressure (preferably 200 to 2000 kPa) stream comprising the expanded first portion of the liquid stream from step (iv) and at least one intermediate pressure (preferably 900 to 2000 kPa) stream comprising the expanded second portion of the liquid stream from step (iv).
- at least one low pressure preferably 200 to 2000 kPa
- at least one intermediate pressure preferably 900 to 2000 kPa
- the amount of expansion of the liquid stream from step (iv) required to provide the necessary cooling duty in step (i) can be minimised, thus also minimising the power required for subsequent compression of the C0 2 product.
- the second portion of the liquid stream from step (iv) is also preferably compressed by known procedures to form a compressed C0 2 product.
- the compressed C0 2 product is suitable for sequestration or for EOR applications.
- the process of the invention further comprises the step of:
- step (vii) expanding and heating a third portion of the liquid stream from step (iv); wherein further cooling in step (i) is provided by heat exchange during heating of the third portion of the liquid stream from step (iv) in step (vii).
- step (i) there are at least three expanded streams which contribute to the cooling of the gaseous feed stream in step (i), namely the first, second and third portions of the liquid stream from step (iv).
- the degree of expansion and the flow rate of each of the first, second and third portions of the liquid stream from step (iv) may be controlled so as to still more closely match the cooling requirements in step (i).
- the third portion of the liquid stream from step (iv) remains at a higher pressure following expansion in step (vi) than both the first and second portions of the liquid stream from step (iv) following expansion in step (v) and step (vi), respectively.
- the third portion of the liquid stream from step (iv) will generally have a pressure in the range of from 1000 to 3000 kPa, more preferably from 1200 to 2500 kPa, and most preferably from 1400 to 2200 kPa.
- the third portion of the liquid stream from step (iv) will generally have a temperature approaching that of the gaseous feed stream, from instance in the range of from -10 to 40 °C, more preferably 0 to 30 °C, for instance 5 to 25 °C. Since the third portion of the liquid stream from step (iv) has the highest pressure after expansion, and thus requires less recompression subsequently to meet product requirements, it is generally desirable for the flow rate of this stream to be maximised within the constraints of the cooling requirements for the feed stream provided by the first and second portions of the liquid stream from step (iv).
- the third portion of the liquid stream from step (iv) comprises the balance of the liquid stream from step (iv).
- the third portion of the liquid stream from step (iv) preferably comprises 20 wt% or more, more preferably 30 wt% or more, still more preferably 40 wt% or more, and most preferably 50 wt% or more of the liquid stream from step (iv).
- cooling in step (i) is thus provided by a low pressure (preferably 200 to 2000 kPa) stream comprising the expanded first portion of the liquid stream from step (iv); an intermediate pressure (preferably 800 to 2500 kPa) stream comprising the expanded second portion of the liquid stream from step (iv); and a high pressure (preferably 1200 to 3000 kPa) stream comprising the expanded third portion of the liquid stream from step (iv);
- a low pressure preferably 200 to 2000 kPa
- an intermediate pressure preferably 800 to 2500 kPa
- a high pressure preferably 1200 to 3000 kPa
- the amount of expansion of the liquid stream from step (iv) required to provide the necessary cooling duty in step (i) can be precisely optimised, thus minimising the power required for subsequent compression of the C0 2 product.
- the second portion of the liquid stream from step (iv) is also preferably compressed by known procedures to form a compressed C0 2 product.
- the compressed C0 2 product is suitable for sequestration or for EOR applications.
- the third portion of the liquid stream from step (iv) comprises the balance of the liquid stream from step (iv).
- the remainder portion of the liquid stream from step (iv) is passed to compression by known procedures to form a compressed C0 2 product, optionally following heat exchange with the gaseous feed stream.
- the compressed C0 2 product is suitable for sequestration or for EOR applications.
- heating of the second and/or third portion of the liquid stream from step (iv) prior to expansion is preferably by heat exchange during cooling of the gaseous feed stream in step (i). In this way, a further contribution is provided to the cooling duty required in step (i). In this way, a further contribution to the cooling of the gaseous feed stream in step (i) is provided.
- compression of more than one C0 2 rich stream to form a compressed C0 2 product.
- Compression of multiple C0 2 rich streams is preferably by way of a multi-stage compression train.
- a number of streams having different pressures may be introduced to the multistage compression train at a stage having the corresponding pressure.
- the expanded first portion of the liquid stream from step (iv) is preferably introduced to a low pressure stage of the multistage compression train; the expanded second portion of the liquid stream from step (iv), where present, is preferably introduced to an intermediate pressure stage of the multistage compression train; the expanded third portion of the liquid stream from step (iv), where present, is preferably introduced to a high pressure stage of the multistage compression train; and the remainder portion of the liquid stream from step (iv), where present, is preferably introduced to a highest pressure stage of the multistage compression train.
- the multiple portions of the liquid stream from step (iv) are recombined in the course of the compression step to provide a combined compressed C0 2 product stream.
- Further compression stages are preferably used to increase the pressure of the C0 2 product stream to the levels required for sequestration and/or EOR applications (i.e. from 10,000 to 20,000 kPa).
- it may be energy efficient to supplement the cooling duty provided by expansion of one or more portions of the liquid stream from step (iv) with an external mechanical refrigeration cycle. In this way, the need for expansion of the liquid stream from step (iv), and hence the power requirements for product gas compression, may be reduced.
- the H 2 rich vapour stream from step (ii) is recovered from the first vapour liquid separator at low temperature, and the process of the invention preferably further comprises the step of:
- step (viii) reheating the H 2 rich vapour stream from step (ii) downstream of the first vapour liquid separator.
- the H 2 rich vapour stream from step (ii) is reheated in heat exchange during cooling of the gaseous feed stream in step (i).
- the H 2 rich vapour stream from step (ii) is reheated to a temperature approaching the temperature of the gaseous feed stream, for instance in the range of from 0 to 40 °C, more preferably from 10 to 30 °C, for example 15 to 20 °C.
- the H 2 rich vapour stream from step (ii) will usually contain a recoverable quantity of C0 2 , in some cases this may be from 10 to 30 mol% of the C0 2 content of the gaseous feed stream. Separation of residual C0 2 from the H 2 rich vapour stream from step (ii) is thus preferred in order to maximise the overall C0 2 recovery from the process.
- the process of the invention further comprises the step of:
- step (ix) passing the reheated H 2 rich vapour stream from step (viii) to a secondary C0 2 separation process to obtain a H 2 rich gas stream.
- the type of secondary C0 2 separation process used in step (ix) is not particularly limited, and known processes such as physical solvent absorption, chemical solvent absorption, membrane separation or pressure swing adsorption (PSA) may be appropriate.
- physical solvent absorption processes may be preferred in many cases, since physical solvent absorption processes are well-suited to the high volume removal of C0 2 from gas streams, particularly where it is not necessary to obtain extremely low levels of residual C0 2 in the gaseous product.
- the overall C0 2 recovery of the process may be increased to 90 mol% or greater of the C0 2 in the gaseous feed stream.
- the recovered C0 2 may be passed to a compression step as described above.
- the C0 2 recovered in step (ix) is preferably passed to an appropriate stage of a multistage compression train whereupon it is recombined with the C0 2 rich streams obtained from step (iv).
- the reheated H 2 rich vapour stream from step viii) is at a pressure which is generally above what is required for downstream combustion of H 2 . Power can thus be recovered from this stream by work-expansion to the pressure required for H 2 fuel gas stream.
- Work expansion of the H 2 rich vapour stream from step (ii) may take place before secondary C0 2 removal in step (ix) or following secondary C0 2 removal. Generally, to avoid unwanted expansion of C0 2 , work expansion preferably takes place following secondary C0 2 removal in step (ix).
- the process of the invention further comprises the step of:
- step (x) work expanding at least a portion of the reheated H 2 rich vapour stream from step (viii) or at least a portion of the H 2 gas stream from step (ix).
- step (x) uses a turbo-compressor linked to a power generator.
- work-expansion of the at least a portion of the reheated H 2 rich vapour stream from step (viii) or the at least a portion of the H 2 gas stream from step (ix) may be used to assist in boosting the pressure of the feed gas, e.g. by way of a turbo- expander having a compressor at the brake end.
- step (x) Following expansion in step (x) a first H 2 fuel gas stream is obtained at a pressure typically suitable for downstream combustion processes.
- the H 2 rich vapour stream from step (iv) is similarly recovered from the second vapour liquid separator at low temperature, and the process of the invention preferably further comprises the step of:
- step (xi) reheating the H 2 rich vapour stream from step (iv) downstream of the second vapour liquid separator to provide a second H 2 fuel gas stream.
- the H 2 rich vapour stream from step (iv) is reheated in heat exchange during cooling of the gaseous feed stream in step (i).
- the H 2 rich vapour stream from step (iv) is reheated to a temperature approaching the temperature of the gaseous feed stream.
- the second H 2 fuel gas stream is preferably combined with the first H 2 fuel gas stream prior to use of the H 2 fuel gas streams in a downstream combustion process.
- the process of the invention further comprises the step of:
- step (xii) is used to drive a turbine to generate power.
- the gaseous feed stream used in the process of the invention is preferably obtained by reforming of a hydrocarbon fuel, such as natural gas, or by gasification of a carbonaceous fuel, such as coal or biomass.
- An additional shift reaction with steam is preferably used to convert carbon monoxide from the reforming/gasification step to additional H 2 and C0 2 .
- the C0 2 and H 2 content of the gaseous feed stream depends on the carbonaceous or hydrocarbon fuel used in the reforming/gasification step. However, the C0 2 content of the gaseous feed stream is generally in the range of from 10 to 60%, and more preferably from 20 to 50 mol%.
- the H 2 content of the gaseous feed stream is generally in the range of from 40 to 90 mol%, and more preferably from 50 to 80 mol%.
- the gaseous feed stream may comprise minor amounts of carbon monoxide (preferably less than 2 mol%), as well as minor amounts of nitrogen (preferably less than 5 mol%) and argon (preferably less than 1 mol%).
- the gaseous feed stream may also comprise minor amounts of methane.
- the amount of methane in the gaseous feed stream is preferably as low as possible since any residual methane in the gaseous feed stream reduces the recovery of carbon (in the form of C0 2 ) from the process.
- the amount of methane in the gaseous feed stream is less than 0.5 mol%, more preferably less than 0.1 mol%, still more preferably less than 0.05 mol%, and most preferably less than 0.02 mol%.
- the gaseous feed stream is treated to remove water prior to step (i), since water is likely to freeze under the operating conditions of the process of the invention, and therefore disrupt the operation of the processing apparatus.
- Water removal is generally by known condensation processes, for example using a multistage compression train with vapour- liquid separators between compression stages to remove condensed water.
- a subsequent drying step over a dessicant, such as molecular sieves is also used to minimise the water content of the gaseous feed stream.
- the water content of the gaseous feed stream is preferably less than 10 ppm by volume, more preferably less than 5 ppm by volume, still more preferably less than 2 ppm by volume, and most preferably less than 1 ppm by volume.
- the gaseous feed stream may also be treated prior to step (i) to remove sulphur containing substances (e.g. H 2 S) and/or mercury.
- sulphur containing substances e.g. H 2 S
- the process of the invention as described above may comprise a number of heat exchange steps.
- the configuration of the heat exchange steps is not particularly limited and may involve separate heat exchangers for each separate heat exchange step, or where appropriate, a number of different heat exchange steps may be combined within a single multistream heat exchanger.
- the present invention provides a separation apparatus for separating C0 2 from a gaseous feed stream comprising C0 2 and H 2 , the apparatus comprising the following parts:
- first vapour-liquid separator adapted to separate the cooled and partially condensed feed stream from part (i) to produce a vapour stream having increased H 2 content relative the feed stream and a liquid stream having increased C0 2 content relative to the feed stream;
- (iii) means for expanding at least a portion of the liquid stream from part (ii);
- a second vapour-liquid separator adapted to separate the expanded stream from part (iii) to produce a vapour stream having increased H 2 content relative the liquid stream from part (ii) and a liquid stream having increased C0 2 content relative to the liquid stream from part (ii);
- (v) means for expanding and heating a first portion of the liquid stream from part (iv);
- the means for cooling in part (i) and the means for heating in part (v) comprises one or more heat exchangers adapted to pass the gaseous feed stream in heat exchange contact with the expanded first portion of the liquid stream from part (iv).
- the first vapour liquid separator is preferably adapted to operate at a temperature in the range of from -30 to -55 °C, more preferably from -40 to -55 °C, still more preferably from -45 to -55 °C, and most preferably from -50 to -55 °C for example -51 °C, -52 °C, -53 °C, or -54 °C.
- the first vapour liquid separator is preferably adapted to operate at pressure in the range of from 2000 to 10,000 kPa, more preferably 3000 to 9000 kPa, and still more preferably from 4000 to 8000 kPa, for example 5000 kPa, 6000 kPa or 7000 kPa.
- the second vapour-liquid separator is preferably also adapted to operate at a temperature in the range of from -30 to -55 °C, more preferably from -40 to -55 °C, still more preferably from -45 to -55 °C, and most preferably from -50 to -55 °C for example -51 °C, -52 °C, -53 °C, or -54 °C.
- the second vapour liquid separator is preferably adapted to operate at a pressure in the range of from 1000 to 6000 kPa, more preferably 2000 to 5000 kPa, for example 3000 kPa or 4000 kPa.
- the apparatus of the invention preferably further comprises means for compressing the expanded, heated first portion of the liquid stream from part (iv) following part (v) to form a compressed C0 2 product.
- the means for expanding the first portion of the liquid stream from part (iv) in part (v) is preferably adapted to expand the first portion of the liquid stream from part (iv) to a pressure in the range of from 200 to 2000 kPa, more preferably 300 to 1500 kPa, still more preferably 400 to 1200 kPa, still more preferably 500 to 1000 kPa, and most preferably 600 to 800 kPa.
- the apparatus of the invention may comprise means for heating the first portion of the liquid stream from part (iv) prior to expansion in part (v).
- the means for heating the first portion of the liquid stream from part (iv) prior to expansion in part (v) comprises one or more heat exchangers adapted to pass the first portion of the liquid stream from part (iv) in heat exchange contact with the gaseous feed stream, to supplement the cooling provided by part (i).
- the apparatus of the invention enables the evaporation of the liquid stream from part (iv) to provide effective cooling of the gaseous feed stream without freezing of the expanded stream due to Joule-Thomson cooling.
- the apparatus of the invention further comprises:
- the means for heating in part (vi) comprises one or more heat exchangers adapted to pass the gaseous feed stream in heat exchange contact with the expanded second portion of the liquid stream from part (iv).
- the apparatus of the invention provides at least two expanded streams to contribute to the cooling of the gaseous feed stream in part (i), namely the first portion of the liquid stream from part (iv) and the second portion of the liquid stream from part (iv).
- the apparatus of the invention comprises means for controlling the degree of expansion and the flow rate of each of the first and second portions of the liquid stream from part (iv) so as to closely match the cooling requirements in part (i).
- the means for expanding the second portion of the liquid stream from part (iv) in part (vi) is adapted to expand the second portion of the liquid stream from part (iv) to a pressure in the range of from 800 to 2500 kPa, more preferably 800 to 2000 kPa, and most preferably 1000 to 1500 kPa.
- the apparatus of the invention preferably further comprises means for compressing the expanded, heated second portion of the liquid stream from part (iv) following part (vi) to form a compressed C0 2 product.
- the apparatus of the invention further comprises:
- the means for heating in part (vii) comprises one or more heat exchangers adapted to pass the gaseous feed stream in heat exchange contact with the expanded third portion of the liquid stream from part (iv).
- the apparatus of the invention provides at least three expanded streams to contribute to the cooling of the gaseous feed stream in part (i), namely the first, second and third portions of the liquid stream from part (iv).
- the apparatus of the invention comprises means for controlling the degree of expansion and the flow rate of each of the first, second and third portions of the liquid stream from part (iv) so as to still more closely match the cooling requirements in part (i).
- the means for expanding the third portion of the liquid stream from part (iv) in part (vi) is adapted to expand the third portion of the liquid stream from part (iv) to a pressure in the range of from 1000 to 3000 kPa, more preferably 1200 to 2500 kPa, and most preferably 1400 to 2200 kPa.
- the apparatus of the invention preferably further comprises means for compressing the expanded, heated third portion of the liquid stream from part (iv) following part (vii) to form a compressed C0 2 product.
- the third portion of the liquid stream from part (iv) comprises the balance of the liquid stream from step (iv).
- the apparatus of the invention may comprise means for compressing a remainder portion of the liquid stream from part (iv) to form a compressed C0 2 product.
- the apparatus may further comprise means for passing the remainder portion of the liquid stream from step (iv) in heat exchange contact with the gaseous feed stream.
- the apparatus of the invention may comprise means for heating the second and/or third portions of the liquid stream from part (iv) prior to expansion in parts (vi) and (vii), respectively.
- the means for heating the second and/or third portions of the liquid stream from part (iv) prior to expansion comprises one or more heat exchangers adapted to pass one or more of the first, second and third portions of the liquid stream from part (iv) in heat exchange contact with the gaseous feed stream, to supplement the cooling provided by part (i).
- the apparatus of the invention may comprise means for compressing more than one C0 2 rich stream to form a compressed C0 2 product.
- the apparatus comprises a multi-stage compression train adapted to compress a number of streams having different pressures by introduction of streams at the stage of the multistage compression train having a corresponding pressure.
- the means for cooling and partially condensing the gaseous feed stream in part (i) may further comprise an external mechanical refrigeration cycle.
- the apparatus of the invention may further comprise:
- (xiii) means for reheating the H 2 rich vapour stream from part (ii) downstream of the first vapour liquid separator.
- the means for reheating the H 2 rich vapour stream from part (ii) comprises one or more heat exchangers adapted to pass the H 2 rich vapour stream from part (ii) in heat exchange contact with the gaseous feed stream, to supplement the cooling provided by part (i).
- the apparatus preferably further comprises:
- the type of secondary C0 2 separation apparatus used in part (ix) is not particularly limited, and known apparatus for physical solvent absorption, chemical solvent absorption, membrane separation or pressure swing absorption (PSA) may be used.
- PSA pressure swing absorption
- the apparatus of the invention further comprises means for compressing separated C0 2 from part (ix) to provide a compressed C0 2 product.
- the means for compressing separated C0 2 from part (ix) comprises a multistage compression train as described above.
- the apparatus of the invention may comprise:
- (xv) means for work expanding at least a portion of the reheated H 2 rich vapour stream from part (viii) or at least a portion of the H 2 gas stream from part (ix).
- the means for work-expanding at least a portion of the heated H 2 rich vapour stream from part (viii) or at least a portion of the H 2 gas stream from part (ix) preferably comprises one or more turbo-expanders.
- the brake end of the turbo-expander may comprise means for generating electricity.
- the brake end of the turbo- expander may comprise a compressor adapted to provide compression for the gaseous feed stream.
- the apparatus comprises means for work expanding at least a portion of the H 2 gas stream from part (ix).
- the apparatus of the invention may further comprise:
- (xvi) means for reheating the H 2 rich vapour stream from part (iv) downstream of the second vapour liquid separator to provide a second H 2 fuel gas stream.
- the means for reheating the H 2 rich vapour stream from part (iv) comprises one or more heat exchangers adapted to pass the H 2 rich vapour stream from part (iv) in heat exchange contact with the gaseous feed stream, to supplement the cooling provided by part (i).
- the apparatus of the invention may further comprise:
- the apparatus of the invention may comprise a number of heat exchangers.
- the configuration of the heat exchangers is not particularly limited and may involve separate heat exchangers for each separate heat exchange step, or where appropriate, a number of different heat exchange steps may be combined within a single multistream heat exchanger.
- Figure 1 shows an embodiment of a separation process and apparatus according to the present invention.
- Figure 2 shows a schematic arrangement of an integrated gasification and carbon capture power generation process and apparatus comprising a separation process and apparatus according to the present invention.
- a gaseous feed stream comprising H 2 and C0 2 (100) is passed to a feed gas compression train (1 10).
- a feed gas compression train (1 10).
- Each compression stage comprises a compressor (120), cooler (130) (typically air or water cooled), and a vapour liquid separator (140) to remove a condensed liquid (150), which comprises substantially water.
- the compressed feed stream (200) is passed to a pre-treatment unit (250), including a molecular sieve dehydration unit to avoid freezing of water in the downstream unit and mercury removal, if necessary, to protect any aluminium equipment.
- the dry feed gas (300) is routed to a high efficiency, multi-stream heat exchanger (310) where it is cooled and partially condensed against returning product streams.
- the cooled two phase stream (315) is passed to a vapour-liquid separator (320) to give a C0 2 rich liquid stream (325) and a hydrogen rich vapour stream (425).
- the hydrogen rich vapour stream (425) is routed back through the heat exchanger (310) at essentially feed gas pressure and is heated close to the feed gas temperature.
- the reheated stream (430) has residual C0 2 content and further processing of this stream in a secondary recovery unit (435) will maximise the recovery of C0 2 .
- the C0 2 stream (440) obtained from the secondary recovery unit (435) is preferably passed to a multi-stage compression train (415) where it is combined with other C0 2 streams (365, 385, 410), and compressed and cooled in stages to provide a C0 2 product stream (420) meeting transportation and/or storage requirements.
- the hydrogen rich stream (445) obtained from the secondary recovery unit (435) is heated (450) and the heated stream (455) is passed to a turbo-expander (460) in order to recover power.
- the C0 2 rich liquid (325) produced in the primary high pressure separator is flashed across a valve (330).
- the resultant two phase stream (335) is separated in a vapour- liquid separator (340) to give a C0 2 rich liquid stream (345) and a further hydrogen rich vapour stream (465), which is routed back through the heat exchanger (310) at intermediate pressure.
- the resulting reheated stream (470) is combined with the main hydrogen fuel gas stream downstream of the turbo expander (460) to provide a hydrogen product stream (480).
- the C0 2 rich liquid stream (345) from the secondary vapour-liquid separator (340) is used to provide cooling to gaseous feed stream though evaporation of reduced pressure streams at a number of pressure levels in the heat exchanger (310).
- three different pressure levels are used: streams (350) and (370) are flashed to intermediate pressures across valves (355) and (375) respectively and the resultant reduced pressure streams (360) and (380) are evaporated and warmed against the feed stream in exchanger (310).
- the remaining fraction of the liquid stream (390) is warmed to an intermediate temperature in the heat exchanger (310) and the intermediate temperature stream (395) is flashed to a low pressure and reduced temperature across a valve (400).
- the resulting stream (405) is then evaporated and warmed in the heat exchanger (310).
- the C0 2 rich product streams (365, 385, 410) are combined at appropriate points within the multi-stage compression train (415), preferably together with the recovered CO 2 stream (440) from the recovery unit (435), and compressed to form a CO 2 product stream (420) meeting transportation and storage requirements.
- Inter- and after-cooling duties within the compressor train are typically provided by air or water.
- a hydrocarbon or carbonaceous fuel (500) is passed to a gasification/reforming stage (510), which is supplied by an air separation unit (520).
- the reformate gas is passed to a shift reaction stage (550) to convert carbon monoxide to CO 2 .
- Subsequent cooling (560) and sulphur dioxide removal (570) stages provide a feed gas comprising H 2 and C0 2 which is suitable for separation according to the process of the invention. If required, sulphur may be recovered from the separated H 2 S in a sulphur recovery stage (580).
- the feed gas is passed to a compression and dehydration stage (590), with further removal of water and optionally mercury in a pretreatment stage (610).
- the resulting gaseous feed stream is passed to separation process/apparatus (610) according to the invention (e.g. as shown in Figure 1 ), comprising a cryogenic separation stage (620).
- a secondary C0 2 recovery stage (630) is used to recover residual C0 2 from the hydrogen rich vapour stream, and an expansion stage (640) is used to recover power from the resulting H 2 rich gas.
- the H 2 rich gas may be passed to a combustion stage (650) to drive a power generation turbine system.
- Combined carbon dioxide streams are passed to a C0 2 compression stage (660) and subsequently to transportation and storage for subsequent sequestration or EOR use (670).
- Table 1 shows typical operating parameters for the process of the invention shown in Figure 1 when used to separate a gaseous mixture consisting of approximately 55.8 mol% hydrogen, 37.9 mol% CO 2 , 1 .7 mol% CO, 3.9 mol% nitrogen, 0.6 mol% argon, 0.1 mol% water and trace amounts of methane.
- Overall CO 2 recovery is 93.7 mol% with a purity of 98.2%.
- Hydrogen recovery is in excess of 99.5 mol%.
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Abstract
La présente invention concerne un procédé et un appareil de séparation, suivant lesquels du CO2 est séparé d'un courant d'alimentation gazeux comprenant du CO2 et du H2, et consiste à : (i) refroidir et condenser partiellement le courant d'alimentation ; (ii) faire passer le courant d'alimentation refroidi et partiellement condensé provenant de l'étape (i) dans un premier séparateur vapeur-liquide pour produire un courant de vapeur ayant une teneur accrue en H2 par rapport au courant d'alimentation et un courant liquide ayant une teneur accrue en CO2 par rapport au courant d'alimentation ; (iii) provoquer l'expansion d'au moins une partie de l'écoulement liquide provenant de l'étape (ii) ; (iv) faire passer le courant expansé provenant de l'étape (iii) dans un second séparateur vapeur-liquide pour produire un courant de vapeur ayant une teneur accrue en H2 par rapport au courant liquide provenant de l'étape (ii) et un courant liquide ayant une teneur accrue en CO2 par rapport au courant liquide provenant de l'étape (ii) ; (v) provoquer l'expansion d'une première partie du courant liquide provenant de l'étape (iv) et chauffer celle-ci, un refroidissement dans l'étape (i) étant prévu au moins en partie par un échange de chaleur pendant un chauffage de la première partie du courant liquide provenant de l'étape (iv) dans l'étape (v).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12719428.0A EP2850375A2 (fr) | 2011-03-16 | 2012-03-15 | Procédé et appareil pour la séparation de dioxyde de carbone et d'hydrogène |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1104454.2A GB2490476B (en) | 2011-03-16 | 2011-03-16 | Process and apparatus for the separation of carbon dioxide and hydrogen |
| GB1104454.2 | 2011-03-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012123752A2 true WO2012123752A2 (fr) | 2012-09-20 |
| WO2012123752A3 WO2012123752A3 (fr) | 2015-02-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2012/050574 Ceased WO2012123752A2 (fr) | 2011-03-16 | 2012-03-15 | Procédé et appareil pour la séparation de dioxyde de carbone et d'hydrogène |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2850375A2 (fr) |
| GB (1) | GB2490476B (fr) |
| WO (1) | WO2012123752A2 (fr) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026310A (zh) * | 2013-03-08 | 2015-11-04 | 乔治洛德方法研究和开发液化空气有限公司 | 用于生产二氧化碳和氢的方法和装置 |
| CN109999529A (zh) * | 2019-04-22 | 2019-07-12 | 中科瑞奥能源科技股份有限公司 | 化工尾气分离回收工艺和装置 |
| WO2019092654A3 (fr) * | 2017-11-09 | 2019-07-18 | 8 Rivers Capital, Llc | Systèmes et procédés de production et de séparation d'hydrogène et de dioxyde de carbone |
| FR3110224A1 (fr) * | 2020-05-18 | 2021-11-19 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de séparation d’un gaz contenant du dioxyde de carbone et de l’hydrogène |
| US11691874B2 (en) | 2021-11-18 | 2023-07-04 | 8 Rivers Capital, Llc | Apparatuses and methods for hydrogen production |
| US11859517B2 (en) | 2019-06-13 | 2024-01-02 | 8 Rivers Capital, Llc | Power production with cogeneration of further products |
| US11891950B2 (en) | 2016-11-09 | 2024-02-06 | 8 Rivers Capital, Llc | Systems and methods for power production with integrated production of hydrogen |
| US12358792B2 (en) | 2023-10-09 | 2025-07-15 | 8 Rivers Capital, Llc | Systems and methods for producing hydrogen with integrated capture of carbon dioxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL2036030B1 (en) | 2023-10-13 | 2025-04-30 | Dens B V | Hydrogen gas production system and method |
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| FR2934170A3 (fr) | 2009-09-28 | 2010-01-29 | Air Liquide | Procede et appareil de separation d'un debit ayant comme un des composants principaux du dioxyde de carbone |
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| DE3313171A1 (de) * | 1983-04-12 | 1984-10-18 | Linde Ag, 6200 Wiesbaden | Verfahren und vorrichtung zur gewinnung von rein-co |
| DE102007007581A1 (de) * | 2007-02-15 | 2008-08-21 | Linde Ag | Verfahren und Vorrichtung zur Trennung eines Gasgemisches |
| US8535417B2 (en) * | 2008-07-29 | 2013-09-17 | Praxair Technology, Inc. | Recovery of carbon dioxide from flue gas |
| US8216344B2 (en) * | 2008-09-26 | 2012-07-10 | Praxair Technology, Inc. | Purifying carbon dioxide using activated carbon |
| US20120167620A1 (en) * | 2009-05-15 | 2012-07-05 | Eva Marfilia Van Dorst | Method and system for separating co2 from synthesis gas or flue gas |
| US9163188B2 (en) * | 2009-07-24 | 2015-10-20 | Bp Alternative Energy International Limited | Separation of carbon dioxide and hydrogen |
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- 2011-03-16 GB GB1104454.2A patent/GB2490476B/en active Active
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- 2012-03-15 EP EP12719428.0A patent/EP2850375A2/fr not_active Withdrawn
- 2012-03-15 WO PCT/GB2012/050574 patent/WO2012123752A2/fr not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2934170A3 (fr) | 2009-09-28 | 2010-01-29 | Air Liquide | Procede et appareil de separation d'un debit ayant comme un des composants principaux du dioxyde de carbone |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026310A (zh) * | 2013-03-08 | 2015-11-04 | 乔治洛德方法研究和开发液化空气有限公司 | 用于生产二氧化碳和氢的方法和装置 |
| US11891950B2 (en) | 2016-11-09 | 2024-02-06 | 8 Rivers Capital, Llc | Systems and methods for power production with integrated production of hydrogen |
| US12054388B2 (en) | 2017-11-09 | 2024-08-06 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
| WO2019092654A3 (fr) * | 2017-11-09 | 2019-07-18 | 8 Rivers Capital, Llc | Systèmes et procédés de production et de séparation d'hydrogène et de dioxyde de carbone |
| US11066298B2 (en) | 2017-11-09 | 2021-07-20 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
| US12240758B2 (en) | 2017-11-09 | 2025-03-04 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
| CN109999529A (zh) * | 2019-04-22 | 2019-07-12 | 中科瑞奥能源科技股份有限公司 | 化工尾气分离回收工艺和装置 |
| US12098658B2 (en) | 2019-06-13 | 2024-09-24 | 8 Rivers Capital, Llc | Cogeneration of chemical products |
| US11859517B2 (en) | 2019-06-13 | 2024-01-02 | 8 Rivers Capital, Llc | Power production with cogeneration of further products |
| FR3110224A1 (fr) * | 2020-05-18 | 2021-11-19 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de séparation d’un gaz contenant du dioxyde de carbone et de l’hydrogène |
| US11814288B2 (en) | 2021-11-18 | 2023-11-14 | 8 Rivers Capital, Llc | Oxy-fuel heated hydrogen production process |
| US12139405B2 (en) | 2021-11-18 | 2024-11-12 | 8 Rivers Capital, Llc | Apparatuses and methods for hydrogen production |
| US12145847B2 (en) | 2021-11-18 | 2024-11-19 | 8 Rivers Capital, Llc | Methods and apparatuses for hydrogen production |
| US11691874B2 (en) | 2021-11-18 | 2023-07-04 | 8 Rivers Capital, Llc | Apparatuses and methods for hydrogen production |
| US12358794B2 (en) | 2021-11-18 | 2025-07-15 | 8 Rivers Capital, Llc | Apparatuses and methods for hydrogen production |
| US12358793B2 (en) | 2021-11-18 | 2025-07-15 | 8 Rivers Capital, Llc | Methods and apparatuses for hydrogen production |
| US12358792B2 (en) | 2023-10-09 | 2025-07-15 | 8 Rivers Capital, Llc | Systems and methods for producing hydrogen with integrated capture of carbon dioxide |
| US12459813B1 (en) | 2023-10-09 | 2025-11-04 | 8 Rivers Capital, Llc | Systems and methods for producing hydrogen with integrated capture of carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2850375A2 (fr) | 2015-03-25 |
| GB2490476A (en) | 2012-11-07 |
| GB2490476B (en) | 2014-09-24 |
| GB201104454D0 (en) | 2011-04-27 |
| WO2012123752A3 (fr) | 2015-02-19 |
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