WO1999013964A1 - Separation of acid gas from combustion gases - Google Patents

Separation of acid gas from combustion gases Download PDF

Info

Publication number
WO1999013964A1
WO1999013964A1 PCT/GB1998/002762 GB9802762W WO9913964A1 WO 1999013964 A1 WO1999013964 A1 WO 1999013964A1 GB 9802762 W GB9802762 W GB 9802762W WO 9913964 A1 WO9913964 A1 WO 9913964A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid
gas
solvent
combustion gas
contactor
Prior art date
Application number
PCT/GB1998/002762
Other languages
French (fr)
Inventor
Bernt Helge Torkildsen
Martin Sigmundstad
Harald Linga
Per Henning Hanssen
Finn Patrick Nilsen
Original Assignee
Den Norske Stats Oljeselskap A.S.
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
Priority claimed from GBGB9719668.7A external-priority patent/GB9719668D0/en
Application filed by Den Norske Stats Oljeselskap A.S. filed Critical Den Norske Stats Oljeselskap A.S.
Priority to AU90866/98A priority Critical patent/AU9086698A/en
Publication of WO1999013964A1 publication Critical patent/WO1999013964A1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1456Removing acid components
    • B01D53/1475Removing carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1456Removing acid components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1493Selection of liquid materials for use as absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/18Absorbing units; Liquid distributors therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/42Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/433Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80Mixing plants; Combinations of mixers
    • B01F33/81Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/002Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00105Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/0011Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00159Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00164Controlling or regulating processes controlling the flow
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to the removal acid gases such as C0 2 , N0 X , H 2 S, oxides of sulphur etc. from combustion gas .
  • acid gases such as C0 2 , N0 X , H 2 S, oxides of sulphur etc.
  • Conventional systems for the absorption of acid gases employ a liquid solvent; typical solvents include amines such as methyldiethanolamine (MDEA) , monoethanolamine (MEA) or diethanolamine (DEA) , and mixtures of solvents. These solvents absorb C0 2 , N0 X , ⁇ oH 2 S and other acid gases.
  • the solvent is contacted with the sour gas mixture (gas mixture including acid gases) in a column which may be a packed column, a plate column or a bubble-cap column, or a column with some other form of contact medium.
  • the gas and liquid include amines such as methyldiethanolamine (MDEA) , monoethanolamine (MEA) or diethanolamine (DEA)
  • 35 acid gas components from combustion gas which comprises: bringing the combustion gas into contact with a liquid including a solvent or reagent for the carbon dioxide and other acid gases; subjecting the natural gas and liquid to turbulent mixing conditions thereby causing the carbon dioxide and other acid gases to be absorbed by the solvent or reagent; and separating a gas phase and a liquid phase.
  • the invention also extends to the apparatus for carrying out this method.
  • the turbulent mixing is very intense and results in extremely efficient gas liquid contact.
  • the mixing regime is preferably turbulent shear layer mixing.
  • the liquid entrained in the gas may be in the form of droplets for gas continuous fluid phase distribution.
  • the efficient mixing means that absorption can take place very rapidly and in a relatively small amount of solvent compared to that required in conventional absorption columns. This in turn means that the liquid duty in the equipment is dramatically reduced resulting in a consequential reduction in the size of any downstream regeneration section.
  • the mixing system used is simple and inexpensive compared to prior art systems, leading to reduced costs. Finally, an efficiency of approaching 100% for the removal of acid gas can be achieved for certain applications.
  • the absorption may be achieved by simply dissolving the gas or by way of a chemical reaction with the solvent .
  • the method is carried ' out as a continuous process with the combustion gas and liquid flowing co-currently .
  • the co-current flow eliminates the problems associated with foaming, since separation can easily be effected downstream of the contactor.
  • the method includes the step of treating the liquid phase to remove the absorbed acid gas components.
  • the turbulent mixing may be achieved by any convenient means, such as ann ejector or a jet pump or more preferably in a turbulent contactor including a gas inlet, a liquid inlet, an outlet leading to a venturi passage and a tube extending from the outlet back upstream, the tube being perforated and/or being spaced from the periphery of the outlet.
  • a turbulent contactor including a gas inlet, a liquid inlet, an outlet leading to a venturi passage and a tube extending from the outlet back upstream, the tube being perforated and/or being spaced from the periphery of the outlet.
  • One suitable contactor is a mixer supplied by Framo Engineering A/S and is described in EP-B-379319.
  • the tube is located in a vessel, the vessel including the gas inlet, the liquid inlet and the outlet.
  • the combustion gas is supplied to the tube, optionally directly, and the liquid is supplied to the vessel, and so the combustion gas stream draws the liquid into the venturi and the two phases are mixed.
  • the combustion as is supplied to the vessel and the liquid is supplied to the tube optionally directly, whereby the combustion gas is drawn into the venturi by the liquid and the two phases are mixed.
  • the liquid and the combustion gas are supplied to the vessel, the liquid being supplied to a level above the level of the outlet, whereby the combustion gas is forced out through the outlet via the tube, thereby drawing the liquid into the venturi so that the two phases are mixed.
  • a solvent absorbs the carbon dioxide and other acid gases .
  • a reagent reacts chemically with the carbon dioxide and other acid gases.
  • the reagent is a biological reagent which removes the carbon dioxide and other acid gases biologically.
  • a plurality of acid gas components are absorbed by a plurality of respective 5 solvents or reagents.
  • the combustion gas and the liquid are formed into a homogeneous mixture in the contactor, the homogeneous mixtures being cooled prior to separation into a gas phase and a liquid phase.
  • the 0 cooled homogeneous mixture is separated into a gas phase and a liquid phase in a hydrocyclone .
  • the solvent in the liquid phase is subjected to a regeneration treatment to remove the absorbed acid gases.
  • the regenerated solvent-containing 5 liquid phase is recycled to the contactor.
  • the regeneration is carried out by heating and/or by flashing off the absorbed gas component in a flash tank.
  • the post-mixing cooling and the regenerative heating are achieved, at least in part by mutual heat o exchange .
  • a portion of the solvent, after extraction, is recycled to the contactor directly, without regeneration.
  • part of the C0 2 - loaded solvent by-passes the regeneration section.
  • This 5 serves to increase the C0 2 loading of the solvent.
  • optimisation of the process may not necessarily relate to the removal efficiency in terms of mole fraction of C0 2 removed, but rather the energy consumption required per unit mass of C0 2 removed.
  • a method for removing acid gases from a combustion gas which comprises : supplying the combustion gas to a turbulent contactor; supplying a liquid including a solvent for the acid gases to the contactor; subjecting the combustion gas and the liquid to turbulent mixing in the contactor to form a homogeneous mixture; allowing the acid gas to be absorbed by the solvent; cooling the homogeneous mixture; separating the cooled homogeneous mixture into a gas phase and a liquid phase in a hydrocyclone (or any other gas/liquid separator); removing the gas phase; subjecting the solvent in the liquid phase to a regeneration treatment to remove the absorbed acid gas; and recycling the regenerated solvent-containing liquid phase to the contactor.
  • a portion of the solvent, after extraction may be recycled directly to the contactor.
  • the regeneration is carried out by heating and/or by flashing off the absorbed gas component in a flash tank.
  • the post mixing cooling and the regenerative heating are achieved, at least in part by mutual heat exchange.
  • the liquid is pumped to the contactor and thereby draws the combustion gas with it through the contactor.
  • the combustion gas is at high pressures, it is conveyed to the contactor at a high pressure and thereby draws the liquid with it through the contactor.
  • the invention also extends to apparatus for carrying out such a method, comprising: a turbulent contactor having a liquid inlet, a gas inlet ' and a fluid outlet; a cooler for the fluid stream from the fluid outlet; a hydrocyclone arranged to separate the cooled fluid stream into a gas phase and a liquid stream; a regenerator arranged to treat the separated liquid stream; and a recycle line arranged to convey the regenerated liquid stream to the contactor.
  • the apparatus may include a recycle line for the liquid stream from the separator to the contactor, by- passing the regenerator.
  • a further separator for example, in the form of a flash tank, in the recycle line to allow absorbed gas to be released from the liquid.
  • the apparatus may include a pump arranged to supply liquid to the liquid inlet of the contactor.
  • the regenerator is a heater and/or a flash tank.
  • the contactor is a turbulent contactor as described above, or alternatively an ejector or a jet pump.
  • the invention may be considered to extend to the use of a turbulent contactor to remove acid gas from natural gas by forming a homogeneous mixture of the gas mixture with a solvent for the acid gas in the contactor, allowing the acid gas to be absorbed by the solvent, and subsequently separating a gas phase and a liquid phase, the liquid phase thereby containing the acid gas.
  • the improved efficiency possible for the removal of acid gases makes the present invention particularly valuable as awareness is increased of the potential damage to the environment that can be caused by acid gases in effluents such as combustion gas .
  • the small size of the apparatus compared to conventional absorption columns render the invention especially applicable to use in marine applications, such as on board shuttle tankers.
  • Figure 1 is a flow diagram of the process for use when the gas is under low pressure
  • Figure 2 is a flow diagram of the process for use when the gas is under high pressure
  • Figure 3 is a block diagram of the apparatus as used in two sets of experiments
  • Figure 4 is a block diagram of the apparatus as used in a third set of experiments.
  • Figure 5 is a view of the turbulent contactor as used in the batch test procedure
  • Figure 6 is a view of an alternative mixer arrangement
  • Figure 7 is a view of a jet pump which can be used as an alternative to the contactor; and Figure 8 is a block diagram of an alternative embodiment of a process according to the invention.
  • a continuous process operation for the removal of carbon dioxide (and other acid gases) from exhaust gas is shown in figure 1.
  • a liquid solvent stream 1 for example MEA (monoethanolamine)
  • MEA monoethanolamine
  • a combustion gas stream 4 including the C0 2 which is to be removed, is drawn into the contactor 3 by the low pressure generated in the venturi by the liquid stream after it has passed through the pump (stream la) .
  • This arrangement provides an automatic means of self-regulation as the gas mixture to solvent ratio can be maintained for varying flow rates.
  • the liquid solvent and the combustion gas stream are in the ' form of a homogeneous mixture (stream 5) and the mass transfer of the C0 2 from the gas phase to the liquid occurs very rapidly.
  • the mixed two phase stream 5 is then conveyed to a cooler 6 and on into a hydro cyclone 7.
  • the gas stream 8 is taken off and the liquid stream 9 passes on to a regeneration system. At this point in the circuit all the C0 2 is in the liquid phase (stream 9) and the gas stream 8 is free of C0 2 .
  • the regeneration of the liquid solvent is achieved by boiling off the C0 2 in a heater 10.
  • the C0 2 is taken off as a gas stream 11 and the liquid solvent is optionally passed through a flash tank (not shown) to remove any residual dissolved gas before being recycled into the feed stream 1.
  • the liquid solvent in stream 1 is topped up from the reservoir 12 as necessary to maintain a regular flow rate around the system.
  • cooler 6 and the heater 10 may be combined to form a heat exchange unit .
  • FIG. 7A n alternative system for the removal of C0 2 from a high pressure combustion gas stream is shown in figure 2.
  • a high pressure combustion gas stream 20 containing the C0 2 which is to be removed is conveyed to a contactor 21 similar to that shown in figure 4.
  • the high pressure of the gas draws a controlled amount of liquid solvent, for example MEA, from the recycle stream 22 and, if necessary, from a reservoir 23 into the contactor 21.
  • the two phases are in the form of a homogeneous mixture (stream 24) and the mass transfer of the C0 2 from the gas phase to the liquid solvent takes place.
  • the residence time may be as little as 0.1 seconds since the reaction kinetics for the absorption of C0 2 by MEA are very rapid, although this will vary with the solvent used and the gas to be transferred from the gas to the liquid.
  • the two phase mixture passes through a cooler 25 to a hydro cyclone unit 26.
  • the gas stream free of C0 2 is taken off in stream 27 and the remaining liquid stream 28 including the C0 2 is passed to a regeneration system.
  • the liquid stream 28 is fed into a heater 29 to remove the C0 2 as a gas stream 30. This regenerates the solvent for re-use in the system.
  • This solvent (stream) is fed into a heater 29 to remove the C0 2 as a gas stream 30. This regenerates the solvent for re-use in the system. This solvent (stream
  • the heater 29 and the cooler 25 can be combined to form a heat exchange unit .
  • the turbulent contactor 100 comprises a vessel 101 having a gas inlet 102, a liquid inlet 103 and an outlet 104 leading to a venturi passage 105.
  • a tube 106 (which may or may not be perforated) extending from the outlet 104 back into the vessel 101.
  • the combustion gas is supplied to the vessel 101 and the liquid solvent is supplied to the tube 106 whereby the gas is drawn into the venturi by the liquid and the two phases are mixed.
  • the liquid solvent is supplied to the vessel 101 and the gas mixture is supplied to the tube 106, whereby the liquid is drawn into the venturi by the gas and the two phases are mixed .
  • the liquid solvent and the combustion gas are supplied to the vessel 101, the solvent being supplied to a level above the level of the outlet 104, whereby the gas is forced out ' through the outlet 104 via the tube 106, thereby drawing the solvent into the venturi so that the two phases are mixed.
  • FIG. 6 A fourth variant is shown in Figure 6. This embodiment is similar to that shown in Figure 5, but the contactor 110 is inverted. It comprises a vessel 111 with a liquid inlet 112, a gas inlet 113 and an outlet 114 leading to a venturi passage 115. There is a tube 116 (which may or may not be perforated) extending from the outlet 114 back into the vessel 111. The tube 116 may be connected directly to the gas inlet 113.
  • FIG. 7 shows a jet pump 120 comprising a first fluid inlet 121 for the high pressure fluid and a second fluid inlet 122 for the low pressure fluid.
  • the high pressure fluid draws the low pressure fluid along the length of the jet pump 120 to the outlet 123.
  • the fluids are well mixed into a homogenised mixture in the region 124 at the outlet of the high pressure inlet 121.
  • FIG. 8 An alternative embodiment is shown in Figure 8.
  • the Co 2 -containing gas is supplied to the contactor 201 via a gas inlet 202 and solvent is supplied via a solvent inlet 203.
  • the two phases are mixed in the contactor 201 and subsequently in a contact pipe 204.
  • the homogeneous mixture is fed via a line 205 to a separator 206 where separation into a cleaned gas stream 207 and a C0 2 loaded solvent stream 208 is effected.
  • the loaded solvent is conveyed to a flash tank 209 where some of the absorbed C0 2 comes out of solution and is removed via line 210.
  • the partially loaded solvent is conveyed to a desorption column 211 via line 212 where the solvent is regenerated and returned to the contactor 201 via line 213.
  • a portion of the partially-loaded solvent is recycled, without regeneration, via recycle line 214, directly to the contactor 201. This serves to increase the loading of the solvent in the system and thus enables the duty of the regeneration operation to
  • the gas stream was a mixture of nitrogen (N 2 ) and C0 2 and the liquid solvent was a mixture of MEA and water.
  • the reservoir pipe was kept under pressure using nitrogen gas.
  • the contactor used was a FRAMO contactor generally as described in EP 379319 and shown in figure 5.
  • the mixer injection pipe was adjusted to yield gas/liquid ratios in the range of about 3 to 5 , depending upon the total flow rate.
  • FIG. 3 A schematic diagram for the series of experiments is shown in figure 3.
  • the contactor 51 is charged with an amount of the liquid solvent mixture from the reservoir 54 which is controlled by a valve 55.
  • a gas source 50 of the experimental N 2 /C0 2 gas mixture is conveyed to the contactor 51 via a pipe 52 controlled by a valve 53.
  • a 1 metre section of pipe 56 in which the mass transfer occurs .
  • This section provides the residence time for the contacting materials.
  • a set of 2 simultaneously acting fast closing valves 57 and 58 form a 1.5 metre analysis section 59 where the gas/liquid mixture can be captured, separated and sampled.
  • At the top end of the analysis section there is a sampling point where a sample of the gas can be drawn off (not shown) .
  • At the lower end of the section there is a further sampling point where a sample of the liquid can be drawn off (not ' shown) .
  • the lower section of the sampling section is provided with means for cooling the liquid sample prior to its removal (not shown for clarity) .
  • a further valve 60 separates the sampling section from a reservoir pipe 61 and is used to control the flow rate through the system.
  • the reservoir pipe 61 is pressurised to a predetermined pressure by an independent nitrogen gas source 62 via a pipe 63 controlled by a valve 64. This pressure will be lower than that in the contactor to provide a pressure difference which will force the fluids through the system.
  • the reservoir pipe 61 is inclined with respect to the horizontal to enable the liquid collected to be drained off via a pipe 65 controlled by a valve 66 to a measurement drum 67 which is used to determine the amount of liquid passing through the system on each run.
  • the drum 67 has a drainage pipe 68 controlled by a valve 69.
  • the contactor 51, pipe section 56 and analysis section 59 are filled with the suitable strength solvent solution.
  • the simultaneously acting valves 57 and 58 are closed and valve 60 is set to a position carefully adjusted to yield the required mass flow rate through the system for the predetermined pressure difference between the contactor and the reservoir pipe.
  • the contactor 51 is pressurised with the test gas of C0 2 -rich nitrogen to a pressure of 50 barg.
  • the reservoir pipe 61 is pressurised with nitrogen to a predetermined value typically between 16 and 48 barg, providing a range of flow rates through the system.
  • test gas is taken to determine the level of C0 2 in the gas.
  • the experiment commences with the activation of the simultaneously operating valves 57 and 58.
  • the liquid and the gaseous solution flow co-currently through the system to the reservoir pipe 61.
  • the pressure in the contactor is maintained at 50 barg during the 10 second test run by manual supply of the test gas from a cylinder fitted with an accurate manometer. This makes it possible to record the amount of spent gas for each experiment .
  • a liquid sample of the amine solution in the analysis section is taken from the lower sampling point. Before the sample is taken the liquid in the analysis section is cooled using nitrogen gas surrounding the pipe section 59. The liquid sample is analyzed using a titration technique specially developed for C0 2 .
  • the gas feed composition was 10.5 mol per cent C0 2 in nitrogen.
  • the only change to the apparatus from the first set of experiments is the addition of a small hydrocyclone at the top of the gas pipe to separate the gas and liquid after reaction. This means that there are no entrained droplets in the gas sample .
  • the liquid solvent mixture is a 50% solution of MEA and the gas feed composition was 9.4 mol per cent C0 2 in nitrogen.
  • the test run lasted for 10 seconds and the pressure in the contactor was maintained by manual supply of the test gas . The results are shown in table 2 below.
  • the gas mixture is exhaust gas from a Yannmar 4TN84E 15 KVA water cooled diesel engine 75.
  • a 30% load was placed on the diesel engine to increase the exhaust gas temperature and to obtain a higher level of C0 2 in the exhaust gas .
  • An orifice plate 74 is provided in pipe 71 for continuous flow measurement of the exhaust gas .
  • a sample of the exhaust gas is taken at point 72 to measure the C0 2 content in the exhaust gas.
  • the valve 70 is closed, allowing exhaust gas to enter the contactor 51.
  • the two valves 57 and 58 are opened simultaneously.
  • the liquid and the gaseous solution flow co-currently through the system for 10 seconds into the reservoir pipe 61 before the valves 57 and 58 are closed simultaneously.
  • a sample of gas from the analysis section 59 is extracted from the upper sampling point immediately after the valves are closed.
  • the sample is tested for content of C0 2 by gas chromatography using a Chromopack Model CP-2002.
  • the expended liquid is released from the reservoir pipe 61 to the measurement drum 67 and weighed.
  • the liquid solvent mixture is a 50% solution of MEA. The results for these tests are shown in Table 3 below:

Abstract

A method of removing carbon dioxide and other acid gas components from combustion gas. The method comprises bringing the combustion gas into contact with a liquid including a solvent or reagent for the carbon dioxide and other acid gases and subjecting the combustion gas and liquid to turbulent mixing conditions thereby causing the carbon dioxide and other acid gases to be absorbed by the solvent or reagent. A gas phase and a liquid phase are then separated.

Description

Separation of Acid Gas from Combustion' Gases The present invention relates to the removal acid gases such as C02, N0X, H2S, oxides of sulphur etc. from combustion gas . 5 Conventional systems for the absorption of acid gases employ a liquid solvent; typical solvents include amines such as methyldiethanolamine (MDEA) , monoethanolamine (MEA) or diethanolamine (DEA) , and mixtures of solvents. These solvents absorb C02, N0X, ιoH2S and other acid gases. The solvent is contacted with the sour gas mixture (gas mixture including acid gases) in a column which may be a packed column, a plate column or a bubble-cap column, or a column with some other form of contact medium. In these systems, the gas and liquid
15 streams flow countercurrently .
The prior art absorption systems suffer the disadvantage that in order to achieve a significant degree of gas/liquid contact, the columns have to be large and their operation is hampered by excessive
20 foaming. In addition, the subsequent stripping section which removes the acid gas from solution must also be large, to handle the large volume of solvent used. Since the operation normally takes place under high pressure and the fluids involved are highly corrosive,
25 the capital costs of the large columns and subsequent stripping section is high. Furthermore, operating costs and maintenance costs are high.
It is an object of the present invention to provide a system for removing acid gas from combustion gas which
30 does not suffer from the disadvantages of the prior art, preferably with a high degree of efficiency and more economically than in existing methods.
According to one aspect of the invention, there is provided a method of removing carbon dioxide and other
35 acid gas components from combustion gas which comprises: bringing the combustion gas into contact with a liquid including a solvent or reagent for the carbon dioxide and other acid gases; subjecting the natural gas and liquid to turbulent mixing conditions thereby causing the carbon dioxide and other acid gases to be absorbed by the solvent or reagent; and separating a gas phase and a liquid phase.
The invention also extends to the apparatus for carrying out this method. The turbulent mixing is very intense and results in extremely efficient gas liquid contact. The mixing regime is preferably turbulent shear layer mixing. The liquid entrained in the gas may be in the form of droplets for gas continuous fluid phase distribution. The efficient mixing means that absorption can take place very rapidly and in a relatively small amount of solvent compared to that required in conventional absorption columns. This in turn means that the liquid duty in the equipment is dramatically reduced resulting in a consequential reduction in the size of any downstream regeneration section. At the same time, the mixing system used is simple and inexpensive compared to prior art systems, leading to reduced costs. Finally, an efficiency of approaching 100% for the removal of acid gas can be achieved for certain applications.
In addition, conventional absorbtion methods involve the evolution of heat which must then be removed from the system. While the method of the invention is capable of operation with a relatively low pressure drop across the mixing means, when greater pressure drop is employed, a cooling effect is achieved and this may render the need for additional cooling unnecessary.
The absorption may be achieved by simply dissolving the gas or by way of a chemical reaction with the solvent . Preferably, the method is carried ' out as a continuous process with the combustion gas and liquid flowing co-currently . The co-current flow eliminates the problems associated with foaming, since separation can easily be effected downstream of the contactor. Preferably, the method includes the step of treating the liquid phase to remove the absorbed acid gas components.
The turbulent mixing may be achieved by any convenient means, such as ann ejector or a jet pump or more preferably in a turbulent contactor including a gas inlet, a liquid inlet, an outlet leading to a venturi passage and a tube extending from the outlet back upstream, the tube being perforated and/or being spaced from the periphery of the outlet. One suitable contactor is a mixer supplied by Framo Engineering A/S and is described in EP-B-379319.
Preferably, the tube is located in a vessel, the vessel including the gas inlet, the liquid inlet and the outlet. In one possible regime, the combustion gas is supplied to the tube, optionally directly, and the liquid is supplied to the vessel, and so the combustion gas stream draws the liquid into the venturi and the two phases are mixed. In another regime, the combustion as is supplied to the vessel and the liquid is supplied to the tube optionally directly, whereby the combustion gas is drawn into the venturi by the liquid and the two phases are mixed. In a third regime, the liquid and the combustion gas are supplied to the vessel, the liquid being supplied to a level above the level of the outlet, whereby the combustion gas is forced out through the outlet via the tube, thereby drawing the liquid into the venturi so that the two phases are mixed. Preferably, a solvent absorbs the carbon dioxide and other acid gases . Alternatively, a reagent reacts chemically with the carbon dioxide and other acid gases. Conceivably, the reagent is a biological reagent which removes the carbon dioxide and other acid gases biologically. In one variant of the invention, a plurality of acid gas components are absorbed by a plurality of respective 5 solvents or reagents.
Preferably, the combustion gas and the liquid are formed into a homogeneous mixture in the contactor, the homogeneous mixtures being cooled prior to separation into a gas phase and a liquid phase. Preferably, the 0 cooled homogeneous mixture is separated into a gas phase and a liquid phase in a hydrocyclone . Preferably, the solvent in the liquid phase is subjected to a regeneration treatment to remove the absorbed acid gases. Preferably, the regenerated solvent-containing 5 liquid phase is recycled to the contactor. Preferably, the regeneration is carried out by heating and/or by flashing off the absorbed gas component in a flash tank. Preferably, the post-mixing cooling and the regenerative heating are achieved, at least in part by mutual heat o exchange .
In one alternative arrangement, a portion of the solvent, after extraction, is recycled to the contactor directly, without regeneration. Thus, part of the C02- loaded solvent by-passes the regeneration section. This 5 serves to increase the C02 loading of the solvent. It should be noted that optimisation of the process may not necessarily relate to the removal efficiency in terms of mole fraction of C02 removed, but rather the energy consumption required per unit mass of C02 removed. By 0 increasing the COs loading of the solvent, it is possible to reduce the amount of solvent that needs to be handled by the regeneration section.
In the case of C02, as the initial solvent loading level is increased, the C02 absorption efficiency drops. 5 However, a considerable fraction of total liquid flow rate can be recirculated directly from the gas liquid separated before the drop in C02 removal becomes significant .
According to a more specific aspect of the invention, there is provided a method for removing acid gases from a combustion gas which comprises : supplying the combustion gas to a turbulent contactor; supplying a liquid including a solvent for the acid gases to the contactor; subjecting the combustion gas and the liquid to turbulent mixing in the contactor to form a homogeneous mixture; allowing the acid gas to be absorbed by the solvent; cooling the homogeneous mixture; separating the cooled homogeneous mixture into a gas phase and a liquid phase in a hydrocyclone (or any other gas/liquid separator); removing the gas phase; subjecting the solvent in the liquid phase to a regeneration treatment to remove the absorbed acid gas; and recycling the regenerated solvent-containing liquid phase to the contactor. Again, a portion of the solvent, after extraction may be recycled directly to the contactor.
Preferably, the regeneration is carried out by heating and/or by flashing off the absorbed gas component in a flash tank. Preferably, the post mixing cooling and the regenerative heating are achieved, at least in part by mutual heat exchange. Preferably, in instances where the combustion gas is at a low pressure, the liquid is pumped to the contactor and thereby draws the combustion gas with it through the contactor. Preferably, when the combustion gas is at high pressures, it is conveyed to the contactor at a high pressure and thereby draws the liquid with it through the contactor.
The invention also extends to apparatus for carrying out such a method, comprising: a turbulent contactor having a liquid inlet, a gas inlet' and a fluid outlet; a cooler for the fluid stream from the fluid outlet; a hydrocyclone arranged to separate the cooled fluid stream into a gas phase and a liquid stream; a regenerator arranged to treat the separated liquid stream; and a recycle line arranged to convey the regenerated liquid stream to the contactor.
The apparatus may include a recycle line for the liquid stream from the separator to the contactor, by- passing the regenerator. There may also be a further separator, for example, in the form of a flash tank, in the recycle line to allow absorbed gas to be released from the liquid.
The apparatus may include a pump arranged to supply liquid to the liquid inlet of the contactor. Preferably, the regenerator is a heater and/or a flash tank. Preferably, the contactor is a turbulent contactor as described above, or alternatively an ejector or a jet pump. The invention may be considered to extend to the use of a turbulent contactor to remove acid gas from natural gas by forming a homogeneous mixture of the gas mixture with a solvent for the acid gas in the contactor, allowing the acid gas to be absorbed by the solvent, and subsequently separating a gas phase and a liquid phase, the liquid phase thereby containing the acid gas.
The improved efficiency possible for the removal of acid gases makes the present invention particularly valuable as awareness is increased of the potential damage to the environment that can be caused by acid gases in effluents such as combustion gas .
Furthermore, the small size of the apparatus compared to conventional absorption columns render the invention especially applicable to use in marine applications, such as on board shuttle tankers.
The invention may be put into practice in various ways and two specific embodiments will be described by way of example to illustrate the invention with reference to the accompanying drawings, in which:
Figure 1 is a flow diagram of the process for use when the gas is under low pressure;
Figure 2 is a flow diagram of the process for use when the gas is under high pressure; Figure 3 is a block diagram of the apparatus as used in two sets of experiments;
Figure 4 is a block diagram of the apparatus as used in a third set of experiments;
Figure 5 is a view of the turbulent contactor as used in the batch test procedure;
Figure 6 is a view of an alternative mixer arrangement ;
Figure 7 is a view of a jet pump which can be used as an alternative to the contactor; and Figure 8 is a block diagram of an alternative embodiment of a process according to the invention.
In one embodiment of the invention, a continuous process operation for the removal of carbon dioxide (and other acid gases) from exhaust gas is shown in figure 1. A liquid solvent stream 1, for example MEA (monoethanolamine) , is conducted by a pump 2 to a contactor 3 (though this could be an ejector) capable of inducing turbulent mixing. A combustion gas stream 4, including the C02 which is to be removed, is drawn into the contactor 3 by the low pressure generated in the venturi by the liquid stream after it has passed through the pump (stream la) . This arrangement provides an automatic means of self-regulation as the gas mixture to solvent ratio can be maintained for varying flow rates. At the outlet of the contactor 3 the liquid solvent and the combustion gas stream are in the ' form of a homogeneous mixture (stream 5) and the mass transfer of the C02 from the gas phase to the liquid occurs very rapidly. The mixed two phase stream 5 is then conveyed to a cooler 6 and on into a hydro cyclone 7. The gas stream 8 is taken off and the liquid stream 9 passes on to a regeneration system. At this point in the circuit all the C02 is in the liquid phase (stream 9) and the gas stream 8 is free of C02.
The regeneration of the liquid solvent is achieved by boiling off the C02 in a heater 10. The C02 is taken off as a gas stream 11 and the liquid solvent is optionally passed through a flash tank (not shown) to remove any residual dissolved gas before being recycled into the feed stream 1. The liquid solvent in stream 1 is topped up from the reservoir 12 as necessary to maintain a regular flow rate around the system.
It will be clear to a person skilled in the art that the cooler 6 and the heater 10 may be combined to form a heat exchange unit .
7An alternative system for the removal of C02 from a high pressure combustion gas stream is shown in figure 2. A high pressure combustion gas stream 20 containing the C02 which is to be removed is conveyed to a contactor 21 similar to that shown in figure 4. The high pressure of the gas draws a controlled amount of liquid solvent, for example MEA, from the recycle stream 22 and, if necessary, from a reservoir 23 into the contactor 21. At the outlet of the contactor 21 the two phases are in the form of a homogeneous mixture (stream 24) and the mass transfer of the C02 from the gas phase to the liquid solvent takes place. The residence time may be as little as 0.1 seconds since the reaction kinetics for the absorption of C02 by MEA are very rapid, although this will vary with the solvent used and the gas to be transferred from the gas to the liquid.
The two phase mixture (stream 24) passes through a cooler 25 to a hydro cyclone unit 26. The gas stream free of C02 is taken off in stream 27 and the remaining liquid stream 28 including the C02 is passed to a regeneration system.
The liquid stream 28 is fed into a heater 29 to remove the C02 as a gas stream 30. This regenerates the solvent for re-use in the system. This solvent (stream
22) is then drawn into the contactor 21 by the low pressure generated in the venturi by the high pressure combustion gas (stream 20) as explained above. Any shortfall in the solvent liquid is made up by addition from the reservoir 23. As in the first embodiment, the heater 29 and the cooler 25 can be combined to form a heat exchange unit .
The contactor used in both the above embodiments is shown in figure 5. The turbulent contactor 100 comprises a vessel 101 having a gas inlet 102, a liquid inlet 103 and an outlet 104 leading to a venturi passage 105.
There is a tube 106 (which may or may not be perforated) extending from the outlet 104 back into the vessel 101.
In a first arrangement, the combustion gas is supplied to the vessel 101 and the liquid solvent is supplied to the tube 106 whereby the gas is drawn into the venturi by the liquid and the two phases are mixed.
In a second arrangement, the liquid solvent is supplied to the vessel 101 and the gas mixture is supplied to the tube 106, whereby the liquid is drawn into the venturi by the gas and the two phases are mixed .
In a third arrangement, the liquid solvent and the combustion gas are supplied to the vessel 101, the solvent being supplied to a level above the level of the outlet 104, whereby the gas is forced out ' through the outlet 104 via the tube 106, thereby drawing the solvent into the venturi so that the two phases are mixed.
A fourth variant is shown in Figure 6. This embodiment is similar to that shown in Figure 5, but the contactor 110 is inverted. It comprises a vessel 111 with a liquid inlet 112, a gas inlet 113 and an outlet 114 leading to a venturi passage 115. There is a tube 116 (which may or may not be perforated) extending from the outlet 114 back into the vessel 111. The tube 116 may be connected directly to the gas inlet 113.
The contactors referred to in the above embodiments may be replaced by jet pump arrangements which are capable of inducing turbulent mixing. Figure 7 shows a jet pump 120 comprising a first fluid inlet 121 for the high pressure fluid and a second fluid inlet 122 for the low pressure fluid. The high pressure fluid draws the low pressure fluid along the length of the jet pump 120 to the outlet 123. The fluids are well mixed into a homogenised mixture in the region 124 at the outlet of the high pressure inlet 121.
An alternative embodiment is shown in Figure 8. Here the Co2-containing gas is supplied to the contactor 201 via a gas inlet 202 and solvent is supplied via a solvent inlet 203. The two phases are mixed in the contactor 201 and subsequently in a contact pipe 204. The homogeneous mixture is fed via a line 205 to a separator 206 where separation into a cleaned gas stream 207 and a C02 loaded solvent stream 208 is effected. The loaded solvent is conveyed to a flash tank 209 where some of the absorbed C02 comes out of solution and is removed via line 210. The partially loaded solvent is conveyed to a desorption column 211 via line 212 where the solvent is regenerated and returned to the contactor 201 via line 213. However, a portion of the partially-loaded solvent is recycled, without regeneration, via recycle line 214, directly to the contactor 201. This serves to increase the loading of the solvent in the system and thus enables the duty of the regeneration operation to be reduced.
The invention is further illustrated by reference to the following examples. These serve to verify the operating principles of the two embodiments described. In a series of batch experiments conducted, the gas stream was a mixture of nitrogen (N2) and C02 and the liquid solvent was a mixture of MEA and water. The reservoir pipe was kept under pressure using nitrogen gas. The contactor used was a FRAMO contactor generally as described in EP 379319 and shown in figure 5. The mixer injection pipe was adjusted to yield gas/liquid ratios in the range of about 3 to 5 , depending upon the total flow rate.
A schematic diagram for the series of experiments is shown in figure 3. The contactor 51 is charged with an amount of the liquid solvent mixture from the reservoir 54 which is controlled by a valve 55. A gas source 50 of the experimental N2/C02 gas mixture is conveyed to the contactor 51 via a pipe 52 controlled by a valve 53.
At the outlet of the contactor 51 there is a 1 metre section of pipe 56 in which the mass transfer occurs . This section provides the residence time for the contacting materials. A set of 2 simultaneously acting fast closing valves 57 and 58 form a 1.5 metre analysis section 59 where the gas/liquid mixture can be captured, separated and sampled. At the top end of the analysis section there is a sampling point where a sample of the gas can be drawn off (not shown) . At the lower end of the section there is a further sampling point where a sample of the liquid can be drawn off (not' shown) . The lower section of the sampling section is provided with means for cooling the liquid sample prior to its removal (not shown for clarity) . A further valve 60 separates the sampling section from a reservoir pipe 61 and is used to control the flow rate through the system. The reservoir pipe 61 is pressurised to a predetermined pressure by an independent nitrogen gas source 62 via a pipe 63 controlled by a valve 64. This pressure will be lower than that in the contactor to provide a pressure difference which will force the fluids through the system. The reservoir pipe 61 is inclined with respect to the horizontal to enable the liquid collected to be drained off via a pipe 65 controlled by a valve 66 to a measurement drum 67 which is used to determine the amount of liquid passing through the system on each run. The drum 67 has a drainage pipe 68 controlled by a valve 69. In operation, the contactor 51, pipe section 56 and analysis section 59 are filled with the suitable strength solvent solution. The simultaneously acting valves 57 and 58 are closed and valve 60 is set to a position carefully adjusted to yield the required mass flow rate through the system for the predetermined pressure difference between the contactor and the reservoir pipe.
The contactor 51 is pressurised with the test gas of C02-rich nitrogen to a pressure of 50 barg. The reservoir pipe 61 is pressurised with nitrogen to a predetermined value typically between 16 and 48 barg, providing a range of flow rates through the system.
Before the experiment starts, a sample of the test gas is taken to determine the level of C02 in the gas. The experiment commences with the activation of the simultaneously operating valves 57 and 58. The liquid and the gaseous solution flow co-currently through the system to the reservoir pipe 61. The pressure in the contactor is maintained at 50 barg during the 10 second test run by manual supply of the test gas from a cylinder fitted with an accurate manometer. This makes it possible to record the amount of spent gas for each experiment .
After 10 seconds the 2 operating valves 57 and 58 are closed simultaneously. A sample of gas from the analysis section is extracted from the upper sampling point immediately after the valves have closed. This is then tested for content of C02 by gas chromatography . The machine used was a Chromopack Model CP-2002 gas chromatograph.
In order to verify the mass balance, a liquid sample of the amine solution in the analysis section is taken from the lower sampling point. Before the sample is taken the liquid in the analysis section is cooled using nitrogen gas surrounding the pipe section 59. The liquid sample is analyzed using a titration technique specially developed for C02.
At the end of each run, the liquid from the reservoir pipe 61 is released into the measurement drum 67 to measure the amount of liquid expended in the course of the run. The results of the tests are shown in Table 1 below:
Figure imgf000016_0001
In all cases the gas feed composition was 10.5 mol per cent C02 in nitrogen.
The results show that virtually all the C02 is absorbed from the gas to the liquid solvent for the 50% and 25% mixture for all the flow rates tested. Only on reduction of the MEA concentration to a mere 5% by weight does the amount of C02 remaining in the gas reach appreciable levels.
From the measurements at the 5% level, it can be seen that the absorption efficiency decreases with an increasing gas flow rate and gas volume fraction. This result is expected since the already lean solvent mixture (only 5% MEA) has a diminishing capacity to absorb all of the C02. The gas chromatograph measurements of the C02 were verified using the data obtained from the titration of the liquid sample. A mass balance calculation on the C02 through the system showed that the C02 which was in the test gas had been transferred to the liquid. In a second set of experiments, the contactor 51 was only pressurised to a low pressure (in the range 0.5 to 2 barg) and the reservoir pipe 61 was left open to atmospheric pressure. This gave a driving force of between 0.5 and 2 bar . The only change to the apparatus from the first set of experiments is the addition of a small hydrocyclone at the top of the gas pipe to separate the gas and liquid after reaction. This means that there are no entrained droplets in the gas sample . In these experiments, the liquid solvent mixture is a 50% solution of MEA and the gas feed composition was 9.4 mol per cent C02 in nitrogen. As for the first set of experiments, the test run lasted for 10 seconds and the pressure in the contactor was maintained by manual supply of the test gas . The results are shown in table 2 below.
Figure imgf000018_0001
(1) -this experiment had a run time of 20 seconds.
The small pressure difference driving the fluids through the system results in there being more liquid relative to the gas than in the previous experiments. Even at these lower gas volume fractions, most of the carbon dioxide is removed from the gas phase. It will be noted that there is no real trend from a pressure difference of 0.5 to 2.0 bar so it will be apparent that this method is applicable down to lower pressure differences than 0.5 bar. Such pressure differences may be present, for example, in exhaust gas systems.
In a third set of experiments, exhaust gas was used in place of the experimental N2/C02 mixture .' A schematic diagram of the apparatus for these experiments is shown in figure 5. In general, the system is operated in a similar way to the system shown in figure 3. As for the first set of experiments, the contactor 51, pipe section 56 and analysis section 59 are charged with an amount of the liquid solvent mixture from the reservoir 54. The exhaust gas comes from a diesel engine 75 and passes through the contactor with a minimum loss of temperature. In contrast to the earlier experiments, the contactor 51 is not pressurised.
In these experiments, the gas mixture is exhaust gas from a Yannmar 4TN84E 15 KVA water cooled diesel engine 75. A 30% load was placed on the diesel engine to increase the exhaust gas temperature and to obtain a higher level of C02 in the exhaust gas . An orifice plate 74 is provided in pipe 71 for continuous flow measurement of the exhaust gas .
Before the experiment starts, a sample of the exhaust gas is taken at point 72 to measure the C02 content in the exhaust gas. In operation, the valve 70 is closed, allowing exhaust gas to enter the contactor 51. When a pressure of approximately 0.4 barg has built up in the contactor, the two valves 57 and 58 are opened simultaneously. As in the previous experiments, the liquid and the gaseous solution flow co-currently through the system for 10 seconds into the reservoir pipe 61 before the valves 57 and 58 are closed simultaneously. A sample of gas from the analysis section 59 is extracted from the upper sampling point immediately after the valves are closed. As before, the sample is tested for content of C02 by gas chromatography using a Chromopack Model CP-2002. At the end of each run the expended liquid is released from the reservoir pipe 61 to the measurement drum 67 and weighed. In these experiments, the liquid solvent mixture is a 50% solution of MEA. The results for these tests are shown in Table 3 below:
Figure imgf000021_0001
Key to Table 3 :
Cx - mol % C02 in exhaust gas
T - Temperature of the exhaust gas (°C) S - Expended solvent (1)
C2 - mol % C02 in exit gas
QG - gas flow rate (m3/hr)
QL - liquid flow rate (m3/b.r)
Qτ - total flow rate (m3/hr) G/L - gas/liquid ratio
As can be seen from the above results, virtually all the C02 is removed from the gas and absorbed into the liquid solvent. It is also clear that the removal efficiency is higher for higher concentrations of C02 in the feed gas which is significant for gas turbine applications. However, the efficiency of the system is still high for low concentrations of C02 in the feed gas. It is noted that there is no significant trend when the temperature of the exhaust gas is varied. This is probably because there is a "quenching effect" when the cool solvent solution contacts the exhaust gas. Reducing the amine flow rate does not significantly change the removal efficiency indicating that the system can be operated with higher gas/liquid ratios, for example higher than 30.
It will be apparent to a person skilled in the art that the results from the three sets of experiments above are not dependent upon the gas to be absorbed or on the solvent used to absorb that gas. Therefore it is clear that the above method of selective transfer of a gas from a mixture of gases to a liquid solvent for that gas is applicable to any gas and any respective solvent.

Claims

Claims :
1. A method of removing carbon dioxide and other acid gas components from combustion gas which comprises : bringing the combustion gas into contact with a liquid including a solvent or reagent for the carbon dioxide and other acid gases; subjecting the combustion gas and liquid to turbulent mixing conditions thereby causing the carbon dioxide and other acid gases to be absorbed by the solvent or reagent; and separating a gas phase and a liquid phase.
2. A method as claimed in Claim 1, in which the method is carried out as a continuous process with the combustion gas and liquid flowing co-currently .
3. A method as claimed in Claim 1 or Claim 2 including the step of treating the liquid phase to remove the absorbed acid gas components.
4. A method as claimed in any preceding Claim, in which the mixing is conducted in a turbulent contactor including a gas inlet, a liquid inlet, an outlet leading to a venturi passage and a tube extending from the outlet back upstream, the tube being perforated and/or being spaced from the periphery of the outlet.
5. A method as claimed in any preceding Claim, in which the tube is located in a vessel, the vessel including the gas inlet, the liquid inlet and the outlet .
6. A method as claimed in Claim 5, in which the combustion gas is supplied to the tube and the liquid is supplied to the vessel, and so the combustion gas stream draws the liquid into the venturi and the two phases are mixed.
7. A method as claimed in Claim 5, in which the combustion gas is supplied to the vessel and the liquid is supplied to the tube, whereby the combustion gas is drawn into the venturi by the liquid and the two phases are mixed.
8. A method as claimed in Claim 5, in which the liquid and the combustion gas are supplied to the vessel, the liquid being supplied to a level above the level of the outlet, whereby the combustion gas is forced out through the outlet via the tube, thereby drawing the liquid into the venturi so that the two phases are mixed.
9. A method as claimed in Claim 2 or Claim 3, in which the mixing is conducted in an ejector.
10. A method as claimed in Claim 9, in which the ejector is a jet pump.
11. A method as claimed in any preceding Claim, in which a solvent absorbs the carbon dioxide and other acid gases .
12. A method as claimed in any of Claims 1 to 10, in which a reagent reacts chemically with the carbon dioxide and other acid gases.
13. A method as claimed in any of Claims 1 to 10, in which the reagent is a biological reagent which removes the carbon dioxide and other acid gases biologically.
14. A method as claimed in any of Claims 1 to 10, in which a plurality of acid gas components are absorbed by a plurality of respective solvents or reagents.
15. A method as claimed in any of Claims 4 to 1 , in which the combustion gas and the liquid are formed into a homogeneous mixture in the contactor, the homogeneous mixtures being cooled prior to separation into a gas phase and a liquid phase.
16. A method as claimed in Claim 15, in which the cooled homogeneous mixture is separated into a gas phase and a liquid phase in a hydrocyclone .
17. A method as claimed in Claim 16, in which the solvent in the liquid phase is subjected to a regeneration treatment to remove the absorbed acid gases .
18. A method as claimed in Claim 17, in which the regenerated solvent-containing liquid phase is recycled to the contactor.
19. A method as claimed in Claim 18, in which the regeneration is carried out by heating and/or by flashing off the absorbed gas component in a flash tank.
20. A method as claimed in Claim 19, in which the post- mixing cooling and the regenerative heating are achieved, at least in part by mutual heat exchange.
21. A method as claimed in any of Claims 17 to 20, in which a portion of the liquid phase is recycled to the contactor without being subjected to a regeneration treatment, thereby by-passing a regeneration section.
PCT/GB1998/002762 1997-09-15 1998-09-14 Separation of acid gas from combustion gases WO1999013964A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU90866/98A AU9086698A (en) 1997-09-15 1998-09-14 Separation of acid gas from combustion gases

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9719668.7 1997-09-15
GBGB9719668.7A GB9719668D0 (en) 1997-09-15 1997-09-15 Acid gas separation
GB9800484.9 1998-01-09
GBGB9800484.9A GB9800484D0 (en) 1997-09-15 1998-01-09 Separation of acid gas from combustion gases

Publications (1)

Publication Number Publication Date
WO1999013964A1 true WO1999013964A1 (en) 1999-03-25

Family

ID=26312261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/002762 WO1999013964A1 (en) 1997-09-15 1998-09-14 Separation of acid gas from combustion gases

Country Status (2)

Country Link
AU (1) AU9086698A (en)
WO (1) WO1999013964A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7507874B2 (en) 2004-08-06 2009-03-24 Pioneer Hi-Bred International, Inc. Genetic loci associated with phytophthora tolerance in soybean
CN109432960A (en) * 2018-11-28 2019-03-08 江门市佐敦环保科技有限公司 A kind of purification device of the exhaust gas containing oxynitrides

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4235607A (en) * 1979-01-19 1980-11-25 Phillips Petroleum Company Method and apparatus for the selective absorption of gases
US4239510A (en) * 1979-01-19 1980-12-16 Phillips Petroleum Company Natural gas purification
US4279628A (en) * 1979-12-31 1981-07-21 Energy Synergistics, Inc. Apparatus for drying a natural gas stream
DE3805157C1 (en) * 1988-02-15 1989-04-06 Mannesmann Ag, 4000 Duesseldorf, De Process for the recovery of light hydrocarbons
WO1990013859A1 (en) * 1989-05-05 1990-11-15 Framo Developments (Uk) Limited Multiphase process mixing and measuring system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4235607A (en) * 1979-01-19 1980-11-25 Phillips Petroleum Company Method and apparatus for the selective absorption of gases
US4239510A (en) * 1979-01-19 1980-12-16 Phillips Petroleum Company Natural gas purification
US4279628A (en) * 1979-12-31 1981-07-21 Energy Synergistics, Inc. Apparatus for drying a natural gas stream
DE3805157C1 (en) * 1988-02-15 1989-04-06 Mannesmann Ag, 4000 Duesseldorf, De Process for the recovery of light hydrocarbons
WO1990013859A1 (en) * 1989-05-05 1990-11-15 Framo Developments (Uk) Limited Multiphase process mixing and measuring system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7507874B2 (en) 2004-08-06 2009-03-24 Pioneer Hi-Bred International, Inc. Genetic loci associated with phytophthora tolerance in soybean
CN109432960A (en) * 2018-11-28 2019-03-08 江门市佐敦环保科技有限公司 A kind of purification device of the exhaust gas containing oxynitrides

Also Published As

Publication number Publication date
AU9086698A (en) 1999-04-05

Similar Documents

Publication Publication Date Title
US6284023B1 (en) Separation of acid gas from natural gas
US7018451B1 (en) Fluid separation system
US6280505B1 (en) Separation of acid gases from gas mixtures
EP1294473B1 (en) Apparatus and method for mixing fluids
US7273513B2 (en) Acid gas removal
AU2001269265A1 (en) Method for mixing fluids
US4853012A (en) Process and device for deacidification of a gas containing H2 S and/or CO2 and mercaptans
WO1999013967A1 (en) Installation for separation of co2 from gas turbine flue gas
KR20170130472A (en) Coalescer for parallel contactor
US6284024B1 (en) Fluid separation system
AU749450B2 (en) Fluid separation system
WO1999013964A1 (en) Separation of acid gas from combustion gases
US10927015B2 (en) Method and apparatus for removal of oxygen from seawater
Carter et al. Bulk CO 2 recovery process
CA2006195A1 (en) High shear jet absorber and gas absorption process

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

NENP Non-entry into the national phase

Ref country code: CA

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase