WO2012092984A1 - Épurateur à vide rotatif - Google Patents

Épurateur à vide rotatif Download PDF

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Publication number
WO2012092984A1
WO2012092984A1 PCT/EP2011/050179 EP2011050179W WO2012092984A1 WO 2012092984 A1 WO2012092984 A1 WO 2012092984A1 EP 2011050179 W EP2011050179 W EP 2011050179W WO 2012092984 A1 WO2012092984 A1 WO 2012092984A1
Authority
WO
WIPO (PCT)
Prior art keywords
core
cylinder
absorbent
outlet
vapour
Prior art date
Application number
PCT/EP2011/050179
Other languages
English (en)
Inventor
Torbjørn FIVELAND
Original Assignee
Statoil Petroleum As
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Statoil Petroleum As filed Critical Statoil Petroleum As
Priority to PCT/EP2011/050179 priority Critical patent/WO2012092984A1/fr
Publication of WO2012092984A1 publication Critical patent/WO2012092984A1/fr

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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
    • B01D53/14—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
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20484—Alkanolamines with one hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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

Definitions

  • the present invention relates to an apparatus and a method for removing and recovering C0 2 from exhaust gases. Furthermore the present invention relates to an apparatus and method for desorption of C0 2 from a liquid absorbent.
  • the conventional method for removing C0 2 from exhaust gas is by use of a standard absorption-desorption process.
  • the gas has its pressure boosted by a blower either before or after an indirect or direct contact cooler.
  • the gas is fed to an absorption tower where the gas is contacted counter-currently with an absorbent flowing downwards.
  • a wash section is fitted to remove, essentially with water, remnants of absorbent following the gas from the C0 2 removal section.
  • the absorbent, rich in C0 2 from the absorber bottom is pumped to the top of a desorption column via a heat recovery heat exchanger rendering the rich absorbent preheated before entering the desorption tower.
  • the C0 2 is stripped by steam, generated in a reboiler positioned at the column bottom.
  • the steam moves up the tower serving as a diluent to the C0 2 although some of the steam condenses to provide desorption heat for the C0 2 .
  • Water and absorbent following C0 2 over the top is recovered in the condenser over the desorber top. Vapour is formed in the reboiler from where the absorbent lean in C0 2 is pumped via the heat recovery heat exchanger and a cooler to the top of the absorption column.
  • EP 0 020 055 Al teaches how e.g. a gas and a liquid can be contacted counter-currently in a rotating packed bed by introducing the liquid at the core of the bed and the gas from the perimeter. It is further known from Ramshaw (Heat Recovery Systems & CHP, vol 13, no 6, pages 493-513, 1993) that a rotating packed bed could also be fitted with a heat exchanger at the outer perimeter, and that this heat exchanger could be used as a reboiler.
  • JP1066420 disclose a system for separation C0 2 from a working fluid employing an absorption fluid.
  • the system comprises two rotating cylinders and injection nozzles arranged there between.
  • a desorption system is not disclosed.
  • the aim of the present invention is to provide a compact desorption system, which is cost efficient both to construct, operate and maintain. It is an aim of the present invention to reduce the thermal degradation of the absorption solution by limiting the residence time of the absorption fluid in the desorber.
  • the present invention aims to increase the efficency of the compact desorption system set forth in the Norwegian patent application NO 20092629 by using one or more enzymes in the process in order to increase the C0 2 transfer rate from a gas comprising C0 2 , to a liquid C0 2 absorbent.
  • the present invention can be utilized in connection with gases coming from different kind of facilities. These facilities could be combined cycle gas fired power plants; coal fired power plants, boilers, cement factories, refineries, the heating furnaces of endothermic processes such as steam reforming of natural gas or similar sources of flue gas containing C0 2 .
  • the present invention can be utilized with any type of liquid C0 2 absorbent, comprising an absorbent and a liquid diluent.
  • applicable absorbents comprise amine based absorbents such as primary, secondary and tertiary amines; one well known example of applicable amines is mono ethanol amine (MEA).
  • MEA mono ethanol amine
  • An other example of an applicable absorbent is potassium carbonate (K 2 CO 3 ) .
  • the liquid diluent is selected among diluents that have a suitable boiling point, are stable and inert towards the absorbent in the suitable temperature and pressure interval.
  • An example of an applicable diluent is water.
  • the enzymes used to increase the C0 2 transfer rate from a gas comprising C0 2 , to a liquid C0 2 absorbent can comprise a carbonic anhydrase (CA).
  • CA carbonic anhydrase
  • a advantageous aspect of the present invention is that it is possible to combine several process equipment items, e.g. five process equipment units, or unit functions, into fewer, possibly one, compact units.
  • the reduced size of the unit or units allows a very compact construction, and the unit or units could be assembled on one skid.
  • the present invention represents a solution to the problem of space in the radial direction and difference in centrifugal acceleration between the inner and outer perimeters, that the present invention also provides integrated condensers at a level right next to or above/below the mass transfer and reboiler zones.
  • the method further involves returning the liquid stream from the main condenser to the core of a cylinder comprising a heated stripper unit, and that the main condenser is rotated around the same axis as the cylinder.
  • the present invention invention may provide solutions for the following problems associated with existing technology:
  • the compact technology uses less material, strongly reduces the piping needs, and removes the need to work high above the ground as is needed for a conventional column. This is expected to strongly reduce the cost of the desorption unit.
  • the customary receiving vessel and reflux pump may be eliminated. These are traditionally standard and thus on the order of 5 conventional units are replaced.
  • the rotating desorber according to the present invention has a very short residence time with little backmixing. Due to this, thermal degradation of the absorbent solution is expected to be significantly reduced.
  • Figure 1 illustrates a rotating desorber according to a first embodiment of the present invention
  • Figure 2 illustrates a rotating assembly according to a second embodiment of the present invention, the rotating assembly comprising an integrated rotating reboiler and desorber packing and stationary condenser;
  • Figure 3 illustrates a reboil desorber according to a third embodiment of the present invention
  • Figure 4 illustrates the use of an absorbent reflux condenser according to a forth embodiment of the present invention
  • Figure 5 illustrates an embodiment of a rotating desorber according to a fifth embodiment of the present invention.
  • a further improvement to the process equipment in the desorption process is the reduction in size. Hence less material is used, less area is needed, and erection is further eased.
  • a first embodiment of the present invention is illustrated on figure 1 showing a cross sectional view along a vertical axis of rotation.
  • the equipment comprises a rotating assembly with two levels. At the lower level there is a stripper unit comprising a rotating packed bed 12 next to the inner core.
  • C0 2 is desorbed from the rich absorbent which is entered through conduit 2 and distributed at the core via nozzles 3.
  • the desorption is achieved mainly by water vapour flowing in a counter-current fashion from the perimeter, and by part of this water vapour condensing thus providing heat for the endothermic desorption of C0 2 .
  • the inward vapour flow 13 is created in a reboiler section 14 forming a periphery part of the stripper unit.
  • a part of the liquid 15, which is lean on C0 2 and moving radial outwards due to the rotation, is evaporated caused by condensing steam on the warm side of this heat
  • the steam 4 referred to is entered at the core and leaves as condensate 6, also at the core after it has supplied heat to reboiler section 14.
  • the liquid 18 is significantly stripped of C0 2 and is allowed to leave the rotating assembly at the outer periphery of the reboiler section 14.
  • the vapour stream 20 reaching the core from the rotating packed bed rises to the upper level where this vapour stream flows outwards in a condenser 16, and where diluent vapour is condensed by a coolant 8 in indirect contact.
  • the heated coolant leaves the condenser at the core as stream 10.
  • the gas stream 24 leaving the condenser 16 is mainly C0 2 and the stream 24 is fit for drying and compression if needed for sequestration.
  • the liquid stream 22 leaving the outer periphery comprises condensed diluent and absorbent and this stream is returned to the core at the lower level via nozzles 5.
  • liquids 2, 22 introduced at the core in the illustrated embodiment are distributed via nozzles.
  • other means of feeding liquids may also be envisaged, such as perforated pipes or similar.
  • Firgure 2 shows a second embodiment of the present invention. Here equal reference numbers are utilized for those parts that are unchanged compared to the first
  • the lower level is unchanged compared to the first embodiment in figure 1, except for a housing 30 that is added illustrating that the upper level is not part of the rotating assembly.
  • the desorber overhead 20 comprising C0 2 , diluent and absorbent is fed to a conventional condenser 116 and brought into indirect contact with a coolant 108.
  • the coolant absorbs heat and leaves through conduit 110.
  • the coolant may be cooling water or another suitable cooling liquid.
  • Liquid condensed in the condenser 116 is returned to the lower level as reflux 22 comprising diluent and absorbent.
  • the vapour stream 124 out of the condenser will contain the desorbed C0 2 fit for drying and compression if needed for
  • a third embodiment of the present invention is shown in figure 3.
  • a desorption section 17 is constructed as a reboiler only without splitting the mass transfer stripping section and the formal reboiler.
  • the reboiler heat transfer area thus doubles as mass transfer area along with the surface of droplets in the section, and all desorption of C0 2 is performed in the reboiler. Since the reboiler design in this invention is by nature a liquid flow through a stripping unit with limited back mixing, the liquid flows radially outwards counter-current to the vapour being created continuously on the reboiler walls.
  • the advantage of this embodiment is a simpler construction compared to the second embodiment illustrated on figure 2.
  • FIG 4 a fourth embodiment of the invention, which could be used with either of the embodiments illustrated on figure 2 or 3, is shown.
  • the further development consists of a reflux condenser 21 positioned between the rotating entity within the housing 30 and the stationary condenser 116.
  • the desorber overhead 20 is fed into the reflux condenser, and the non-condensed parts of this stream are fed into the main condenser 116.
  • the condensate from the main condenser 116 is fed as stream 25 into the top of the reflux condenser 21.
  • the combined liquid condensate streams are returned to the lower level via conduit 22. This leads to a small distillation taking place.
  • the cold condensate from the main condenser 116 may be routed to some other point of advantage in the process thus reducing the need for heat supply to the reboiler equivalent to heating said condensate to the lean absorbent temperature.
  • the reflux condenser described could be fitted into the core of the rotating entity on the lower level, and rotating with the entity and some condensate from the condenser could be used for reflux.
  • the rotating axis could also be horizontally aligned.
  • the speed of rotation will make the liquids travel radially thereby forcing the vapour phase to move towards the axis of rotation.
  • Figure 5 shows another embodiment of the present invention where the axis of rotation is horizontally aligned.
  • the embodiment has many similarities with the embodiments shown on figure 1 and 3.
  • Figure 5 illustrates the directions of flow in this embodiment. Similar elements are referred to with similar reference numbers with an addition of 300 for the reference numbers to be distinctive.
  • FIG. 5 shows an integrated tubular reboiler and stripper.
  • the reboiler unit 317 is designed with a number of small diameter tubes for heat supply. Steam is supplied trough conduit 304 and passed trough the tubes running in parallel with the axis of rotation. The tubes are in communication with a conduit 306 for removing the condensate. For the purpose of illustration three tubes are shown on each side of the axis of rotation, however the reboiler may comprise any number of tubes.
  • the stripper is integrated in the reboiler. The C0 2 rich absorbent is introduced via conduit 302 and the stripping will take place when the absorbent solution is introduced to unit 317.
  • Depleted absorbent solution leaves the reboiler unit 317 at the circumference as stream 318. Whereas the vapour phase including the C0 2 leaves the reboiler near the centre into conduit 320 and directed into a first condenser 316 at the perimeter.
  • it is proposed in one aspect of the invention to include layers of thin metal mesh between the rows of reboiler tubes, e.g 6 mm tubes in 9 mm centre diameter will give a reboiler specific surface of 233 m 2 /m 3.
  • a fine metal mesh with wire diameter 0.5-1 mm diameter gives specific surface areas above 1000 m 2 /m 3 depending on mesh spacing.
  • the small tubes can be fixed to the end plates using conventional roller expander techniques.
  • This solution requires that the tubes are open in both ends with condensate drainage in the end closest to the condenser section 316.
  • the condensate may be removed in a fluid mechanical seal located on the stator cylinder at the same axial position, instead of using special return channels to the stator end cover.
  • sieve trays or perforated plates are included between the rows of tubes for heat supply instead of thin metal mesh , the sieve trays/perforated plates will increase the area of liquid gas contact and also contribute to enhanced distribution of the liquid phase.
  • small spherical "pellets" are included between the rows of tubes.
  • the embodiment illustrated on figure 5 comprises a two stage condenser 326 and 346. Cooling liquid is entered at the centre through conduit 308 and supplied first to the second condenser 346 and thereafter onto the first condenser 316 before the cooling liquid leaves through conduit 310 arranged at the centre. In another aspect of the present invention the cooling liquid is supplied through conduits along the centre but with inlet and outlet from the reboiler side. In the first condenser 316 diluent and absorbent is condensed and will due to the rotation be transported to the perimeter where it leaves the condenser 316 as stream 322. Stream 322 may be returned to the reboiler 317 as reflux.
  • the second condenser 346 mainly diluent free of absorbent is condensed and leaves the condenser as stream 342. If water is used as diluent the obtained water stream from the second condenser may in one aspect of the present invention be utilized as washing liquid in the absorption process to remove traces of the absorbent from the C0 2 depleted gas stream.
  • the stream 324 out of the condenser will contain the desorbed C0 2 fit for drying and compression if needed for sequestration.
  • one or more enzymes can be utilized to increase the C0 2 transfer rate from a gas comprising C0 2 , to a liquid C0 2 absorbent.
  • one or more enzymes e.g. carbonic anhydrase (CA)
  • CA carbonic anhydrase
  • CA exists in a number of variants.
  • the turnover rate (number of reactions at a single active site) for the most active variants of CA is about 10 6 C0 2 molecules per second.
  • a rough estimate is that in a process CA may speed up the hydration rate of dissolved C0 2 10-50 times compared to chemical hydration rate under the same conditions.
  • the process temperature may be a limitation, but the use of for example modified mesophilic enzymes and/or enymes from thermophilic prokaryotes may increases the possible process temperatures to at least 80-100 °C.
  • the enzymes may be dispersed in the liquid C0 2 absorbent.
  • the process stability of immobilized CA is on the order of weeks to months, inter alia depending on residence times and temperature in the stripper.
  • the absorbent which contains enzymes
  • the absorbent is heated for only 10-20 seconds before it is cooled. In the conventional process used for stripping, the absorbent is heated for 3-5 minutes.
  • the short residence times that are possible according to the present invention, increases the lifetime of the enzymes used in the process considerably and thereby increases the feasability of using enzymes.
  • the stripper operates at a pressure in the range of 0.6 - 0.9 bars and at a temperature in the range of 40 - 100 °C, and preferably in a range of 70 - 95 °C.
  • the low pressure will also result in an enhanced flashing of C0 2 .
  • a lower temperature will tend to increase the duration of the process stability of CA

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

La présente invention concerne un système de désorption du CO2 à partir d'un fluide d'absorption comprenant un cylindre dont la partie centrale intérieure est ouverte ainsi qu'une unité d'épuration entre la partie centrale ouverte et, là où la garniture (17) est disposée de façon à tourner autour d'un axe à travers la partie centrale, un conduit (2) d'alimentation en fluide d'absorption riche en CO2 de la partie centrale de la garniture, une sortie d'absorbant pauvre (18) au niveau du périmètre du cylindre de matériel de garniture, un dispositif d'alimentation indirecte en chaleur (4, 6) d'au moins une partie périphérique du matériel de garniture et une sortie de vapeur (20) disposée au niveau de la partie centrale d'une première extrémité du cylindre. Selon la présente invention, au moins une enzyme est dispersée dans le fluide d'absorption. En outre, la présente invention concerne une méthode de désorption de CO2.
PCT/EP2011/050179 2011-01-07 2011-01-07 Épurateur à vide rotatif WO2012092984A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2011/050179 WO2012092984A1 (fr) 2011-01-07 2011-01-07 Épurateur à vide rotatif

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2011/050179 WO2012092984A1 (fr) 2011-01-07 2011-01-07 Épurateur à vide rotatif

Publications (1)

Publication Number Publication Date
WO2012092984A1 true WO2012092984A1 (fr) 2012-07-12

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9216377B1 (en) 2015-02-24 2015-12-22 Chevron U.S.A. Inc. Method and system for removing impurities from gas streams using rotating packed beds
WO2018017792A1 (fr) 2016-07-20 2018-01-25 Novozymes A/S Anhydrases carboniques métagénomiques thermostables et leur utilisation
CN108355587A (zh) * 2018-03-09 2018-08-03 中建安装工程有限公司 一种模块化旋转填料床
WO2024118901A2 (fr) 2022-11-30 2024-06-06 Novozymes A/S Variants d'anhydrase carbonique et polynucléotides codant pour ceux-ci

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0020055A1 (fr) 1979-05-31 1980-12-10 Imperial Chemical Industries Plc Procédé et dispositif pour effectuer un échange de masses
US4283255A (en) * 1977-12-01 1981-08-11 Imperial Chemical Industries Limited Mass transfer process
US4627890A (en) * 1981-11-24 1986-12-09 Imperial Chemical Industries Plc Centrifugal device
JPS6466420A (en) 1987-09-08 1989-03-13 Mitsui Shipbuilding Eng Separation device of working fluid after cleaning and carbon dioxide gas absorbing fluid for closed circuit type diesel engine
US7740689B2 (en) * 2005-02-24 2010-06-22 Co2 Solution Inc. CO2 absorption solution
NO20092629A1 (no) 2009-07-10 2011-01-11 Statoil Asa Roterende desorpsjonshjul

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283255A (en) * 1977-12-01 1981-08-11 Imperial Chemical Industries Limited Mass transfer process
EP0020055A1 (fr) 1979-05-31 1980-12-10 Imperial Chemical Industries Plc Procédé et dispositif pour effectuer un échange de masses
US4627890A (en) * 1981-11-24 1986-12-09 Imperial Chemical Industries Plc Centrifugal device
JPS6466420A (en) 1987-09-08 1989-03-13 Mitsui Shipbuilding Eng Separation device of working fluid after cleaning and carbon dioxide gas absorbing fluid for closed circuit type diesel engine
US7740689B2 (en) * 2005-02-24 2010-06-22 Co2 Solution Inc. CO2 absorption solution
NO20092629A1 (no) 2009-07-10 2011-01-11 Statoil Asa Roterende desorpsjonshjul
WO2011005118A1 (fr) * 2009-07-10 2011-01-13 Statoil Asa Roue de désorbeur rotatif

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAMSHAW, HEAT RECOVERY SYSTEMS & CHP, vol. 13, no. 6, 1993, pages 493 - 513

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9216377B1 (en) 2015-02-24 2015-12-22 Chevron U.S.A. Inc. Method and system for removing impurities from gas streams using rotating packed beds
WO2018017792A1 (fr) 2016-07-20 2018-01-25 Novozymes A/S Anhydrases carboniques métagénomiques thermostables et leur utilisation
CN108355587A (zh) * 2018-03-09 2018-08-03 中建安装工程有限公司 一种模块化旋转填料床
CN108355587B (zh) * 2018-03-09 2023-08-29 中建安装集团有限公司 一种模块化旋转填料床
WO2024118901A2 (fr) 2022-11-30 2024-06-06 Novozymes A/S Variants d'anhydrase carbonique et polynucléotides codant pour ceux-ci

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