CA2769495C - Process for removing harmful substances from carbon dioxide and apparatus for the performance thereof - Google Patents
Process for removing harmful substances from carbon dioxide and apparatus for the performance thereof Download PDFInfo
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- CA2769495C CA2769495C CA2769495A CA2769495A CA2769495C CA 2769495 C CA2769495 C CA 2769495C CA 2769495 A CA2769495 A CA 2769495A CA 2769495 A CA2769495 A CA 2769495A CA 2769495 C CA2769495 C CA 2769495C
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- carbon dioxide
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- harmful substances
- liquid carbon
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000126 substance Substances 0.000 title claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 71
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 19
- 230000000274 adsorptive effect Effects 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052756 noble gas Inorganic materials 0.000 claims abstract description 4
- 150000002731 mercury compounds Chemical class 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000003464 sulfur compounds Chemical class 0.000 claims 1
- 150000002835 noble gases Chemical class 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—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 condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/22—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/416—Further details for adsorption processes and devices involving cryogenic temperature treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
- Carbon And Carbon Compounds (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
A process for removing harmful substances from a gas stream which comprises essentially carbon dioxide CO2, and also comprises substances of value, such as at least one of the gases hydrogen H2, carbon monoxide CO, nitrogen N2 or noble gases, and harmful substances such as a substance from the group of mercury, sulphur, mercury compounds or sulphur compounds, wherein a carbon dioxide condensation is performed in order to obtain liquid carbon dioxide, adsorptive removal of the harmful substances from the condensed carbon dioxide is performed to remove the harmful substances from the carbon dioxide, and a process temperature of less than -30°C but greater than -70°C is maintained.
Description
Process for removing harmful substances from carbon dioxide and apparatus for the performance thereof FIELD OF INVENTION
The invention relates to a process and to an apparatus for = separating harmful substances from a carbon dioxide stream.
Compounds of sulfur or mercury are examples of harmful substances.
BACKGROUND
On account of the so-called greenhouse effect and the global temperature rise associated therewith, the emission of greenhouse gases into the atmosphere is subject to increasing criticism. A considerable proportion of the greenhouse effect is attributed to carbon dioxide CO2 which is produced during the combustion of fossil fuels.
There is currently a consensus across society that separating out carbon dioxide from power station waste gases may counteract an increase in the greenhouse effect. For this reason, corresponding further developments are directed at making possible plants having low levels of carbon dioxide emissions or even none at all. Accordingly, the latest concepts for power stations having low levels of carbon dioxide emissions or which are free of carbon dioxide emissions are at the development stage. All of these concepts pursue the common objective of separating the carbon dioxide as completely as possible and at a high level of purity with minimal energy consumption.
Here the focus is on the separation of the carbon dioxide in the first instance. In addition, however, further undesirable substances are present which occur depending on the type of
The invention relates to a process and to an apparatus for = separating harmful substances from a carbon dioxide stream.
Compounds of sulfur or mercury are examples of harmful substances.
BACKGROUND
On account of the so-called greenhouse effect and the global temperature rise associated therewith, the emission of greenhouse gases into the atmosphere is subject to increasing criticism. A considerable proportion of the greenhouse effect is attributed to carbon dioxide CO2 which is produced during the combustion of fossil fuels.
There is currently a consensus across society that separating out carbon dioxide from power station waste gases may counteract an increase in the greenhouse effect. For this reason, corresponding further developments are directed at making possible plants having low levels of carbon dioxide emissions or even none at all. Accordingly, the latest concepts for power stations having low levels of carbon dioxide emissions or which are free of carbon dioxide emissions are at the development stage. All of these concepts pursue the common objective of separating the carbon dioxide as completely as possible and at a high level of purity with minimal energy consumption.
Here the focus is on the separation of the carbon dioxide in the first instance. In addition, however, further undesirable substances are present which occur depending on the type of
2 fuel and which need to be removed. Sulfur, mercury or their compounds are the most commonly encountered substances in terms of quantity in this context.
The latest power station concepts include general conditions which in each case provide the most advanced techniques for separating harmful substances according to the current prior art.
According to the prior art, harmful substances which accumulate in power stations, such as sulfur or mercury compounds, are removed directly from the gas phase. Thus, hydrogen sulfide, for example, is separated by means of gas scrubbing. This entails routing the gas stream through an absorber in which a liquid medium absorbs the harmful substances. Liquid absorber media are for example aqueous alkanolamine solutions, specifically aqueous methyl diethanolamine, or for example cold methanol, employed in the Rectisol process. Such processes using liquid absorber media are known and established in various technologies.
Disadvantages in the prior art consist primarily in the fact that gas scrubbing processes involve an increased energy requirement because they may be associated with process steps such as compression and/or cooling.
The regeneration of absorber media is accomplished by means of distillation, with which a substantial degree of energy consumption is associated.
Furthermore, processes of said type are relatively complicated in terms of infrastructure and setup, which has disadvantageous implications in relation to process = CA 02769495 2014-04-07
The latest power station concepts include general conditions which in each case provide the most advanced techniques for separating harmful substances according to the current prior art.
According to the prior art, harmful substances which accumulate in power stations, such as sulfur or mercury compounds, are removed directly from the gas phase. Thus, hydrogen sulfide, for example, is separated by means of gas scrubbing. This entails routing the gas stream through an absorber in which a liquid medium absorbs the harmful substances. Liquid absorber media are for example aqueous alkanolamine solutions, specifically aqueous methyl diethanolamine, or for example cold methanol, employed in the Rectisol process. Such processes using liquid absorber media are known and established in various technologies.
Disadvantages in the prior art consist primarily in the fact that gas scrubbing processes involve an increased energy requirement because they may be associated with process steps such as compression and/or cooling.
The regeneration of absorber media is accomplished by means of distillation, with which a substantial degree of energy consumption is associated.
Furthermore, processes of said type are relatively complicated in terms of infrastructure and setup, which has disadvantageous implications in relation to process = CA 02769495 2014-04-07
3 implementation and investment costs.
SUMMARY
The object of some embodiments of the invention is to describe an energy-saving option for removing harmful substances in power stations which are substantially fired by fossil fuels. It is furthermore intended to disclose an easy-to-use apparatus for performing the process.
Some embodiments of the invention are based on the fact that in the case of a gas mixture which in large part consists of carbon dioxide CO2 and includes proportions of valuable gases and harmful substances, particularly in the case of condensation of the carbon dioxide, the harmful substances preferably accumulate in the liquid carbon dioxide. This knowledge is exploited to the effect that the separation of the harmful substances from the liquid phase of the carbon dioxide takes place at low temperatures through the use of adsorber materials/adsorbents, preferably solid adsorber materials. In this case it is particularly advantageous that the energy balance associated with separating harmful substances at low temperatures turns out to be positive, in other words the overall energy requirement is less.
The separation of the harmful substances from the liquid phase can take place at low temperatures very advantageously by means of adsorber materials because the materials employed here have large surface areas which are available for the absorption of the harmful substances.
If the process for separating harmful substances from a gas stream consisting substantially of carbon dioxide is combined with a process in which carbon dioxide is already present in liquid form, synergistic effects in the overall energy balance
SUMMARY
The object of some embodiments of the invention is to describe an energy-saving option for removing harmful substances in power stations which are substantially fired by fossil fuels. It is furthermore intended to disclose an easy-to-use apparatus for performing the process.
Some embodiments of the invention are based on the fact that in the case of a gas mixture which in large part consists of carbon dioxide CO2 and includes proportions of valuable gases and harmful substances, particularly in the case of condensation of the carbon dioxide, the harmful substances preferably accumulate in the liquid carbon dioxide. This knowledge is exploited to the effect that the separation of the harmful substances from the liquid phase of the carbon dioxide takes place at low temperatures through the use of adsorber materials/adsorbents, preferably solid adsorber materials. In this case it is particularly advantageous that the energy balance associated with separating harmful substances at low temperatures turns out to be positive, in other words the overall energy requirement is less.
The separation of the harmful substances from the liquid phase can take place at low temperatures very advantageously by means of adsorber materials because the materials employed here have large surface areas which are available for the absorption of the harmful substances.
If the process for separating harmful substances from a gas stream consisting substantially of carbon dioxide is combined with a process in which carbon dioxide is already present in liquid form, synergistic effects in the overall energy balance
4 can thereby be achieved.
It is particularly advantageous to set and maintain the process temperature at less than -30 C. It is not beneficial to use temperatures below -70 C because carbon dioxide exists in the solid phase at such low temperatures.
The process pressure must in principle lie above the triple point of carbon dioxide in accordance with the temperature/pressure diagram. It is thus at least 5 bar. A
temperature range which can likewise be used for the process temperature begins at -5 C and extends toward lower temperatures.
The use of the process for separating harmful substances from a gas mixture which substantially consists of carbon dioxide can be implemented particularly advantageously in so-called zero-carbon dioxide power stations. In said power stations the separation of the carbon dioxide can be carried out cryogenically. With this approach the carbon dioxide is brought to a low temperature, liquefied and separated out. The liquid phase is very well suited for the adsorptive separation of harmful substances because the latter by preference accumulate in the liquid carbon dioxide. Furthermore, low temperatures promote adsorption, which means for example that a gas scrubbing stage as provided in the prior art is no longer necessary. The use of fixed-bed adsorbers for the adsorption of harmful substances is advantageous because solids having a large surface area are employed here. These are in particular alumina (aluminum oxide), activated carbon, silica gel, zeolites or polymers having a large surface area.
Since the surface area of the adsorbents becomes populated with harmful substances in the course of the process, a periodic regeneration of individual fixed-bed adsorbers is advantageously provided.
According to one aspect of the present invention, there is
It is particularly advantageous to set and maintain the process temperature at less than -30 C. It is not beneficial to use temperatures below -70 C because carbon dioxide exists in the solid phase at such low temperatures.
The process pressure must in principle lie above the triple point of carbon dioxide in accordance with the temperature/pressure diagram. It is thus at least 5 bar. A
temperature range which can likewise be used for the process temperature begins at -5 C and extends toward lower temperatures.
The use of the process for separating harmful substances from a gas mixture which substantially consists of carbon dioxide can be implemented particularly advantageously in so-called zero-carbon dioxide power stations. In said power stations the separation of the carbon dioxide can be carried out cryogenically. With this approach the carbon dioxide is brought to a low temperature, liquefied and separated out. The liquid phase is very well suited for the adsorptive separation of harmful substances because the latter by preference accumulate in the liquid carbon dioxide. Furthermore, low temperatures promote adsorption, which means for example that a gas scrubbing stage as provided in the prior art is no longer necessary. The use of fixed-bed adsorbers for the adsorption of harmful substances is advantageous because solids having a large surface area are employed here. These are in particular alumina (aluminum oxide), activated carbon, silica gel, zeolites or polymers having a large surface area.
Since the surface area of the adsorbents becomes populated with harmful substances in the course of the process, a periodic regeneration of individual fixed-bed adsorbers is advantageously provided.
According to one aspect of the present invention, there is
5 provided a process for separating a harmful substance from a gas mixture which essentially consists of carbon dioxide as well as a recyclable substance, comprising: carrying out a carbon dioxide condensation in order to produce and to separate liquid carbon dioxide; carrying out an adsorptive separation of the harmful substance from the liquid carbon dioxide in order to remove the harmful substance from the liquid carbon dioxide;
wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation; and setting a process temperature in a range from -30 C to -70 C.
According to another aspect of the present invention, there is provided an apparatus for separating a harmful substance from a gas mixture which essentially consists of carbon dioxide as well as a recyclable substance, comprising: a carbon dioxide condensation unit to produce and to separate liquid carbon dioxide; and a fixed-bed adsorber for carrying out an adsorptive separation of the harmful substance from liquid carbon dioxide in order to remove the harmful substances from the liquid carbon dioxide, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70 C to -30 C.
5a According to another aspect of the present invention, there is provided a power station comprising: a cryogenic carbon dioxide separation unit to provide cryogenically separated liquid carbon dioxide; an apparatus for separating a harmful substance from a mixture which essentially consists of liquid carbon dioxide as well as a recyclable substance, the apparatus comprising: a fixed-bed adsorber for the adsorptive separation of the harmful substance from liquid carbon dioxide for the purpose of removing the harmful substances therefrom, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70 C to -30 C.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments will be described in the following with reference to schematic accompanying figures, in which specifically:
5b Figure 1 schematically illustrates a fixed-bed adsorber through which liquid carbon dioxide containing harmful substances is fed, the harmful substances being adsorbed in the fixed-bed adsorber.
Figure 2 illustrates adsorbers connected in parallel which can be switched over individually or in groups between the adsorption and regeneration operating states by means of corresponding valves.
DETAILED DESCRIPTION
The adsorption of harmful substances is carried out in fixed-bed adsorbers, such as are illustrated in Figures 1 and 2.
After a certain period of use it is necessary to regenerate the adsorbents. This is effected by means of a reduction in pressure, an increase in temperature, or by feeding through a gas or vapor, or by a combination thereof. For this reason there exist a plurality of adsorbers which are in operation or can be regenerated on an alternating basis. An arrangement of three fixed-bed adsorbers is illustrated in Figure 2.
Analogous configurations for two or more than three adsorbers are possible.
During the carbon dioxide condensation a substantial accumulation of harmful substances contained in a gas mixture occurs automatically in the liquid carbon dioxide. It has been
wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation; and setting a process temperature in a range from -30 C to -70 C.
According to another aspect of the present invention, there is provided an apparatus for separating a harmful substance from a gas mixture which essentially consists of carbon dioxide as well as a recyclable substance, comprising: a carbon dioxide condensation unit to produce and to separate liquid carbon dioxide; and a fixed-bed adsorber for carrying out an adsorptive separation of the harmful substance from liquid carbon dioxide in order to remove the harmful substances from the liquid carbon dioxide, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70 C to -30 C.
5a According to another aspect of the present invention, there is provided a power station comprising: a cryogenic carbon dioxide separation unit to provide cryogenically separated liquid carbon dioxide; an apparatus for separating a harmful substance from a mixture which essentially consists of liquid carbon dioxide as well as a recyclable substance, the apparatus comprising: a fixed-bed adsorber for the adsorptive separation of the harmful substance from liquid carbon dioxide for the purpose of removing the harmful substances therefrom, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70 C to -30 C.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments will be described in the following with reference to schematic accompanying figures, in which specifically:
5b Figure 1 schematically illustrates a fixed-bed adsorber through which liquid carbon dioxide containing harmful substances is fed, the harmful substances being adsorbed in the fixed-bed adsorber.
Figure 2 illustrates adsorbers connected in parallel which can be switched over individually or in groups between the adsorption and regeneration operating states by means of corresponding valves.
DETAILED DESCRIPTION
The adsorption of harmful substances is carried out in fixed-bed adsorbers, such as are illustrated in Figures 1 and 2.
After a certain period of use it is necessary to regenerate the adsorbents. This is effected by means of a reduction in pressure, an increase in temperature, or by feeding through a gas or vapor, or by a combination thereof. For this reason there exist a plurality of adsorbers which are in operation or can be regenerated on an alternating basis. An arrangement of three fixed-bed adsorbers is illustrated in Figure 2.
Analogous configurations for two or more than three adsorbers are possible.
During the carbon dioxide condensation a substantial accumulation of harmful substances contained in a gas mixture occurs automatically in the liquid carbon dioxide. It has been
6 possible to demonstrate this with the aid of simulation calculations taking as example hydrogen sulfide H2S and also carbonyl sulfide COS. The harmful substances can subsequently be separated out from the liquid phase at low temperatures by mans of adsorber materials.
The energy-saving separation of the harmful substances at lower temperatures in the overall concept is advantageous. A
process according to the invention can be excellently combined with a power station concept which already provides cryogenic carbon dioxide separation.
The temperature range for operating the process can lie between -5 C and -70 C. The lower temperature limit lies in the region of the solidification of carbon dioxide from the liquid phase, which means that solids can block the process.
As a general rule it is necessary to ensure that the fixed-bed adsorbers are kept open for the liquid reaction stream.
However, the energy balance of the entire process reveals that temperatures of -30 C and lower are advantageous for the separation of harmful substances.
The valuable gases such as hydrogen, carbon monoxide, nitrogen or noble gases which may be present in the gaseous or liquid stream in the process are not adsorbed in the course of the described process approach. Harmful substances such as mercury, sulfur or their compounds, which are to be found substantially in the liquid carbon dioxide stream, accumulate on the surface in the fixed-bed adsorbers, in other words are adsorbed by the adsorbents, and are thus retained in the fixed-bed adsorbers. A further harmful substance which can be separated out in this manner is carbonyl sulfide COS.
The energy-saving separation of the harmful substances at lower temperatures in the overall concept is advantageous. A
process according to the invention can be excellently combined with a power station concept which already provides cryogenic carbon dioxide separation.
The temperature range for operating the process can lie between -5 C and -70 C. The lower temperature limit lies in the region of the solidification of carbon dioxide from the liquid phase, which means that solids can block the process.
As a general rule it is necessary to ensure that the fixed-bed adsorbers are kept open for the liquid reaction stream.
However, the energy balance of the entire process reveals that temperatures of -30 C and lower are advantageous for the separation of harmful substances.
The valuable gases such as hydrogen, carbon monoxide, nitrogen or noble gases which may be present in the gaseous or liquid stream in the process are not adsorbed in the course of the described process approach. Harmful substances such as mercury, sulfur or their compounds, which are to be found substantially in the liquid carbon dioxide stream, accumulate on the surface in the fixed-bed adsorbers, in other words are adsorbed by the adsorbents, and are thus retained in the fixed-bed adsorbers. A further harmful substance which can be separated out in this manner is carbonyl sulfide COS.
7 Figure 1 shows a fixed-bed adsorber 1 into which a liquid carbon dioxide stream 2 containing harmful substances is introduced. A liquid carbon dioxide stream 3 free of harmful substances emerges at the outlet of the fixed-bed adsorber 1.
Figure 2 shows three fixed-bed adsorbers 1 connected in parallel. The liquid carbon dioxide stream 2 is supplied at the top, harmful substances are captured in the fixed-bed adsorbers 1, and the liquid carbon dioxide stream 3 free of harmful substances can be removed at the bottom. Individual fixed-bed adsorbers 1 can be switched over in each case for regeneration purposes 4.
While a direct catalytic conversion may be associated with a favorable state of equilibrium on account of the low temperatures, it does however exhibit very unfavorable kinetics. Very large quantities of catalysts would be required, which would probably become very rapidly deactivated due to the presence of sulfur.
Figure 2 shows three fixed-bed adsorbers 1 connected in parallel. The liquid carbon dioxide stream 2 is supplied at the top, harmful substances are captured in the fixed-bed adsorbers 1, and the liquid carbon dioxide stream 3 free of harmful substances can be removed at the bottom. Individual fixed-bed adsorbers 1 can be switched over in each case for regeneration purposes 4.
While a direct catalytic conversion may be associated with a favorable state of equilibrium on account of the low temperatures, it does however exhibit very unfavorable kinetics. Very large quantities of catalysts would be required, which would probably become very rapidly deactivated due to the presence of sulfur.
Claims (10)
1. A process for separating a harmful substance from a gas mixture which essentially consists of carbon dioxide as well as a recyclable substance, comprising:
carrying out a carbon dioxide condensation in order to produce and to separate liquid carbon dioxide;
carrying out an adsorptive separation of the harmful substance from the liquid carbon dioxide in order to remove the harmful substance from the liquid carbon dioxide;
wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation; and setting a process temperature in a range from -30°C to -70°C.
carrying out a carbon dioxide condensation in order to produce and to separate liquid carbon dioxide;
carrying out an adsorptive separation of the harmful substance from the liquid carbon dioxide in order to remove the harmful substance from the liquid carbon dioxide;
wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation; and setting a process temperature in a range from -30°C to -70°C.
2. The process as claimed in claim 1, wherein the recyclable substance contained in the gas mixture is selected from the group consisting of hydrogen, carbon monoxide, nitrogen, and a noble gas.
3. The process as claimed in any one of claims 1 and 2, wherein the harmful substance contained in the gas mixture is selected from the group consisting of sulfur, mercury, sulfur compounds and mercury compounds.
4. The process as claimed in any one of claims 1 to 3, wherein at least one substance for an adsorbent for the adsorptive separation of the harmful substance is selected from the group consisting of activated carbon, zeolite, silica gel, alumina and at least one polymer having a large surface area.
5. The process as claimed in anyone of claims 1 to 4, wherein the separation of at least one harmful substance from carbon dioxide takes place in low- or zero-carbon dioxide power stations.
6. A power station comprising:
a cryogenic carbon dioxide separation unit to provide cryogenically separated liquid carbon dioxide;
an apparatus for separating a harmful substance from a mixture which essentially consists of liquid carbon dioxide as well as a recyclable substance, the apparatus comprising:
a fixed-bed adsorber for the adsorptive separation of the harmful substance from liquid carbon dioxide for the purpose of removing the harmful substances therefrom, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70°C to -30°C.
a cryogenic carbon dioxide separation unit to provide cryogenically separated liquid carbon dioxide;
an apparatus for separating a harmful substance from a mixture which essentially consists of liquid carbon dioxide as well as a recyclable substance, the apparatus comprising:
a fixed-bed adsorber for the adsorptive separation of the harmful substance from liquid carbon dioxide for the purpose of removing the harmful substances therefrom, wherein the recyclable substance remains in the liquid carbon dioxide exiting the adsorptive separation, and wherein the operating temperature of the apparatus lies in a range from -70°C to -30°C.
7. The power station as claimed in claim 6, wherein for the purpose of the adsorptive separation, the fixed-bed adsorber includes at least one adsorbent selected from the group consisting of activated carbon, zeolite, alumina and a polymer having a large surface area.
8. The power station as claimed in any one of claims 6 and 7, wherein a plurality of fixed-bed adsorbers having adsorbents are present, and wherein the plurality of fixed-bed adsorbers are connectable in parallel in groups, such that adsorbers or groups of adsorbers are capable of being switched over to allow regeneration of the adsorbents.
9. The power station as claimed in any one of claim 6 to 8, wherein the recyclable substance is selected from the group consisting of hydrogen, carbon monoxide, nitrogen, and a noble gas.
10. The power station as claimed in any one of claims 6 to 9, wherein the harmful substance is selected from the group consisting of mercury, sulfur, and compounds thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009035389.5 | 2009-07-30 | ||
| DE102009035389A DE102009035389A1 (en) | 2009-07-30 | 2009-07-30 | Process for pollutant removal from carbon dioxide and apparatus for carrying it out |
| PCT/EP2010/060335 WO2011012470A1 (en) | 2009-07-30 | 2010-07-16 | Process for removing harmful substances from liquid carbon dioxide and apparatus for performance thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2769495A1 CA2769495A1 (en) | 2011-02-03 |
| CA2769495C true CA2769495C (en) | 2018-05-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2769495A Expired - Fee Related CA2769495C (en) | 2009-07-30 | 2010-07-16 | Process for removing harmful substances from carbon dioxide and apparatus for the performance thereof |
Country Status (10)
| Country | Link |
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| US (1) | US20120144860A1 (en) |
| EP (1) | EP2459293A1 (en) |
| KR (1) | KR20120055576A (en) |
| CN (1) | CN102470287B (en) |
| AU (1) | AU2010277760B2 (en) |
| BR (1) | BR112012001719A2 (en) |
| CA (1) | CA2769495C (en) |
| DE (1) | DE102009035389A1 (en) |
| RU (1) | RU2551510C2 (en) |
| WO (1) | WO2011012470A1 (en) |
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| DE102010006102A1 (en) | 2010-01-28 | 2011-08-18 | Siemens Aktiengesellschaft, 80333 | Process for the separation of purified value gas from a gas mixture, and apparatus for carrying out this process |
| US9458022B2 (en) | 2014-03-28 | 2016-10-04 | L'Air Liquide Société Anonyme Pour L'Étude Et L'Exploitation Des Procedes Georges Claude | Process and apparatus for separating NO2 from a CO2 and NO2—containing fluid |
| US11135542B2 (en) | 2016-10-28 | 2021-10-05 | Uop Llc | Processes and apparatuses for removing contaminants from hydrogen streams |
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| US2039330A (en) * | 1930-07-08 | 1936-05-05 | Ralph H Mckee | Purification of carbon dioxide |
| US3074245A (en) * | 1957-07-18 | 1963-01-22 | Linde Eismasch Ag | Process for the selective removal of carbon dioxide and hydrogen sulfide from gaseous mixtures containing the same |
| US3001373A (en) * | 1958-04-11 | 1961-09-26 | Texaco Inc | Separation of carbon dioxide from gaseous mixtures |
| US3421984A (en) * | 1967-05-02 | 1969-01-14 | Susquehanna Corp | Purification of fluids by selective adsorption of an impure side stream from a distillation with adsorber regeneration |
| US4052176A (en) * | 1975-09-29 | 1977-10-04 | Texaco Inc. | Production of purified synthesis gas H2 -rich gas, and by-product CO2 -rich gas |
| US4270937A (en) * | 1976-12-01 | 1981-06-02 | Cng Research Company | Gas separation process |
| US4144038A (en) * | 1976-12-20 | 1979-03-13 | Boc Limited | Gas separation |
| US4759848A (en) * | 1985-01-23 | 1988-07-26 | Mg Industries | Sterilization of cryogenic liquids by ultrafiltration |
| US4784672A (en) * | 1987-10-08 | 1988-11-15 | Air Products And Chemicals, Inc. | Regeneration of adsorbents |
| US5100635A (en) * | 1990-07-31 | 1992-03-31 | The Boc Group, Inc. | Carbon dioxide production from combustion exhaust gases with nitrogen and argon by-product recovery |
| US5837032A (en) * | 1991-01-30 | 1998-11-17 | The Cynara Company | Gas separations utilizing glassy polymer membranes at sub-ambient temperatures |
| US5271760A (en) * | 1993-03-01 | 1993-12-21 | Uop | Recovery of liquid mercury from process streams |
| US5450728A (en) * | 1993-11-30 | 1995-09-19 | Air Products And Chemicals, Inc. | Recovery of volatile organic compounds from gas streams |
| RU2125480C1 (en) * | 1994-02-15 | 1999-01-27 | Ростовская-на-Дону государственная академия строительства | Method of cleaning flue gases from gaseous contaminating components |
| WO1996015304A1 (en) * | 1994-11-09 | 1996-05-23 | R.R. Street & Co. Inc. | Method and system for rejuvenating pressurized fluid solvents used in cleaning substrates |
| US5743929A (en) * | 1995-08-23 | 1998-04-28 | The Boc Group, Inc. | Process for the production of high purity carbon dioxide |
| FR2774006B1 (en) * | 1998-01-23 | 2000-02-18 | Air Liquide | INSTALLATION AND METHOD FOR FILTERING THE LIQUID PHASE OF A CRYOGENIC FLUID |
| US6511528B1 (en) * | 1999-03-26 | 2003-01-28 | Uop Llc | Purification of carbon dioxide |
| US6361696B1 (en) * | 2000-01-19 | 2002-03-26 | Aeronex, Inc. | Self-regenerative process for contaminant removal from liquid and supercritical CO2 fluid streams |
| EP1441836A4 (en) * | 2001-10-17 | 2006-04-19 | Praxair Technology Inc | Central carbon dioxide purifier |
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| RU2440179C2 (en) * | 2005-03-17 | 2012-01-20 | НОКС II ИНТЕНЭШНЛ, эЛТиДи. | Method of reducing content of sulphur and/or mercury in flue gases (versions), sorbent composition, method of burning coal with reduced emission of harmful elements into environment (versions), coal ash obtained using said methods, and cement, pozzolan, concrete mixture and mortar thereof, concrete structure, method of producing cementing mixture, obtained based on or through said ash |
| US7556671B2 (en) * | 2005-08-08 | 2009-07-07 | The Boc Group, Inc. | System and method for purifying a gas |
| ES2604080T3 (en) * | 2007-01-17 | 2017-03-02 | Union Engineering A/S | High purity carbon dioxide recovery procedure |
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| FR2918578B1 (en) * | 2007-07-13 | 2010-01-01 | Air Liquide | PROCESS FOR PURIFYING GAS CONTAINING CO2 |
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-
2009
- 2009-07-30 DE DE102009035389A patent/DE102009035389A1/en not_active Withdrawn
-
2010
- 2010-07-16 US US13/384,616 patent/US20120144860A1/en not_active Abandoned
- 2010-07-16 CA CA2769495A patent/CA2769495C/en not_active Expired - Fee Related
- 2010-07-16 AU AU2010277760A patent/AU2010277760B2/en not_active Ceased
- 2010-07-16 WO PCT/EP2010/060335 patent/WO2011012470A1/en active Application Filing
- 2010-07-16 CN CN201080032593.XA patent/CN102470287B/en not_active Expired - Fee Related
- 2010-07-16 BR BR112012001719A patent/BR112012001719A2/en not_active Application Discontinuation
- 2010-07-16 EP EP10734117A patent/EP2459293A1/en not_active Withdrawn
- 2010-07-16 RU RU2012107387/05A patent/RU2551510C2/en not_active IP Right Cessation
- 2010-07-16 KR KR1020127005360A patent/KR20120055576A/en not_active Application Discontinuation
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|---|---|
| WO2011012470A1 (en) | 2011-02-03 |
| US20120144860A1 (en) | 2012-06-14 |
| RU2012107387A (en) | 2013-09-10 |
| AU2010277760B2 (en) | 2015-02-19 |
| BR112012001719A2 (en) | 2016-04-12 |
| DE102009035389A1 (en) | 2011-02-03 |
| CN102470287A (en) | 2012-05-23 |
| EP2459293A1 (en) | 2012-06-06 |
| KR20120055576A (en) | 2012-05-31 |
| CA2769495A1 (en) | 2011-02-03 |
| AU2010277760A1 (en) | 2012-02-02 |
| CN102470287B (en) | 2015-09-30 |
| RU2551510C2 (en) | 2015-05-27 |
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