CN102695935A - Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid - Google Patents

Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid Download PDF

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Publication number
CN102695935A
CN102695935A CN2010800247790A CN201080024779A CN102695935A CN 102695935 A CN102695935 A CN 102695935A CN 2010800247790 A CN2010800247790 A CN 2010800247790A CN 201080024779 A CN201080024779 A CN 201080024779A CN 102695935 A CN102695935 A CN 102695935A
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Prior art keywords
carbon dioxide
oxygen
stream
rich
argon
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CN2010800247790A
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Chinese (zh)
Inventor
J-P·特拉尼耶
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of CN102695935A publication Critical patent/CN102695935A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/006—Layout of treatment plant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
    • F23L7/007—Supplying oxygen or oxygen-enriched air
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    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
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    • F25J3/04533—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the direct combustion of fuels in a power plant, so-called "oxyfuel combustion"
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    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
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    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/0489—Modularity and arrangement of parts of the air fractionation unit, in particular of the cold box, e.g. pre-fabrication, assembling and erection, dimensions, horizontal layout "plot"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/18—Noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • F23J2900/00—Special arrangements for conducting or purifying combustion fumes; Treatment of fumes or ashes
    • F23J2900/15061—Deep cooling or freezing of flue gas rich of CO2 to deliver CO2-free emissions, or to deliver liquid CO2
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    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/32—Direct CO2 mitigation
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

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  • Thermal Sciences (AREA)
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  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)
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  • Treating Waste Gases (AREA)

Abstract

The invention relates to a method for producing an argon-enriched fluid and an oxygen-enriched fluid from a fluid resulting from a method for purifying of oxy-fuel combustion fumes, wherein said method comprises purifying the residual gas by a purification method in order to produce a gas enriched with carbon dioxide (119) and a residual gas lean in carbon dioxide (120), pretreating the residual gas lean in carbon dioxide in order to obtain a flow enriched with carbon dioxide and a flow (123) lean in carbon dioxide, treating the flow lean in carbon dioxide by a cryogenic technique so as to extract at least an argon-enriched fraction (127), an oxygen-enriched fraction (126), and a fraction (125) lean in argon and/or oxygen.

Description

Be used for producing the method and apparatus of at least a stream with rich argon body and at least a oxygen-rich fluid from residual fluid
Technical field
The present invention relates to be used for producing the method for at least a stream with rich argon body and at least a oxygen-rich fluid from residue/residual fluid; This residual fluid results from the method that is used to purify residual gas, residual gas comprise carbon dioxide and argon and oxygen or argon and oxygen one of them.Special example does, produces argon from the not condensables of the method that is used for cryogenic separation residual gas (residual gas is produced by the equipment of oxygen consumed), and said residual gas is the oxy-fuel combustion flue gas.
Background technology
Thermo-power station make can be through fuel combustion release heat, heat can be used to produce steam and mechanical or electrical energy.Combustion product gases is with a large amount of CO 2Discharge into the atmosphere.In order to solve this environmental problem, present solution comprises, in the boiler that has oxygen enrichment and gas most important denitrogenation, burns.This burning produces has high concentration CO 2Combustion product gases, this is favourable because with from having low concentration CO 2Flue gas in remove CO 2Compare, be used for removing CO from combustion product gases 2Prior art more easily from having high concentration CO 2Flue gas in remove CO 2Then, before isolating, need be to this CO 2Purify and compress.
Summary of the invention
An object of the present invention is to provide a kind of from be rich in carbon dioxide and comprise argon and/or the residual gas of oxygen produce argon and oxygen method, this argon and oxygen are to be used for removing at low temperatures CO 2Not condensables with the unit of flue.
A theme of the present invention provides a kind of at least a method that is rich in the fluid and the oxygen containing fluid of at least a richness of argon of from residual fluid, producing; This residual fluid results from the method that is used to purify residual gas; This residual gas comprises carbon dioxide and oxygen and/or argon; This residual gas is from the equipment that is supplied to the oxygen that contains argon, and this equipment is oxy-fuel combustion equipment, and this method may further comprise the steps:
-reclaiming the residual gas of forming by flue gas, flue gas results from fuel in the combustion chamber of boiler by means of being rich in oxygen and carbon dioxide and containing the oxygen-enriched combusting of the gas of argon;
-purify residual gas, particularly leave the flue gas of boiler through the purification method under the low temperature particularly, so that produce the residual fluid that the fluid that is rich in carbon dioxide and carbon dioxide become poorness;
The residual fluid that the said carbon dioxide of-preliminary treatment becomes poor is so that obtain to be rich in the stream and the poor stream of carbon dioxide of carbon dioxide; With
The stream that-K cryogenic treatment carbon dioxide is poor is rich in the become part of poorness of the part of argon, rich oxygen containing part and at least one argon and/or oxygen so that from this stream, extract at least one.
According to other optional aspect:
The poor stream of-K cryogenic treatment carbon dioxide comprises: step of in reversible or regeneration type (regeneration type) interchanger, cooling off in condenser, alternatively in reboiler, alternatively at least one interchanger, alternatively and the step of in destilling tower, distilling;
-preferably carry out purification method at low temperatures, although can substitute with other known purification method (for example washing) through amine;
The poor stream of-carbon dioxide is carbonated not basically, and can contain the for example carbon dioxide of several ppm;
-in air-separating plant, preferably through separating air by cryogenic distillation, so that produce rich oxygen containing stream, rich oxygen containing stream comprises maximum 99% oxygen; Preferably comprise maximum 98% or the maximum oxygen of 97mol%; Rich oxygen containing stream also comprises argon, preferably comprises the argon of 2mol% at least, or the argon of 3mol% at least; And should the oxygen containing stream of richness be transported to the equipment of oxygen consumed, be preferably used for oxy-fuel combustion;
The oxygen containing part of-Fu is used for the oxygen-enriched combusting of fuel and/or is used for the preliminary treatment of the residual gas that carbon dioxide becomes poor;
-handle also to make the recyclable part that is rich in nitrogen;
-from be used for from the unit of air divided gas flow or be used for separation of air gas, carry a kind of or more kinds of fluid of unit of at least a portion of the oxygen that is used for oxy-fuel combustion to be used to handle the poor stream of carbon dioxide;
The poor stream of-carbon dioxide is cooled at the upper reaches of K cryogenic treatment, and the poor stream of carbon dioxide is carbonated not basically;
The poor stream of-carbon dioxide is cooled at the upper reaches of K cryogenic treatment, and the poor stream of carbon dioxide is cleaned to remove carbon dioxide simultaneously, and the poor stream of carbon dioxide comprises carbon dioxide;
The poor stream of-carbon dioxide is cooled at least one reversible interchanger or regeneration type interchanger, and the stream that produces is transferred the tower to the K cryogenic treatment unit;
A kind of in-these fluids is the liquid that is rich in nitrogen, and this liquid that is rich in nitrogen keeps the cooling of the low-temperature process of the poor stream of carbon dioxide at least in part;
-be not used in or in turbine, expand from the fluid of the tower of processing unit;
The poor stream of-carbon dioxide is transferred to first tower (first tower has bottom reboiler alternatively); And it is separated and form rich oxygen containing fluid and be rich in the fluid of nitrogen; And extract intermediate flow and be delivered to the bottom of second tower from first tower, form the part that is rich in argon thereby in second tower, make this intermediate flow be rich in argon;
-extract the part that is rich in argon and flow to denitrification column from second tower, so that form rich argon part;
-from be used for from the unit of air divided gas flow or be used for the gas of separation of air, a kind of or more kinds of fluid of unit of at least a portion of carrying the equipment that is used to be supplied oxygen for example to be used for the oxygen of oxy-fuel combustion is used to handle the poor stream of carbon dioxide;
-be used for being contained in the single ice chest from least one tower of the unit of air divided gas flow and at least one tower of processing unit;
A kind of in-these fluids is the gas that is rich in nitrogen, and this gas that is rich in nitrogen will be as at least one reboiler of K cryogenic treatment and/or the recyclegas of at least one condenser;
-before K cryogenic treatment, the carbon dioxide of at least 50% even basic 100% in the residual gas is removed in preliminary treatment;
-carry out preliminary treatment through the anti-sublimation/distillation of carbon dioxide in a plurality of parallelly connected interchangers at least in part;
-under the situation that has oxygen enrichment partly to exist, carry out the distillation of carbon dioxide, thus the oxygen-enriched combusting of carbon dioxide/oxygen mixture formed for use in fuel;
-carry out preliminary treatment through TSA, PSA or VPSA process at least in part, become the poor part that still is rich in argon so that produce the part and the carbon dioxide that are rich in carbon dioxide;
-carry out preliminary treatment through absorption process at least in part;
-absorption process is used the aqueous solution of alkaline ph value;
-through injecting NaOH and/or Na 2CO 3And/or NH 3Obtain alkaline ph value;
-carry out preliminary treatment through adsorption process at least in part;
-carry out preliminary treatment through infiltration at least in part;
-be circulated to boiler by the stream that is rich in carbon dioxide of preliminary treatment generation, preferably be circulated to the combustion chamber.
Another theme of the present invention provides a kind of at least a fluid of argon and device of the oxygen containing fluid of at least a richness of being rich in of from residual fluid, producing; This residual fluid results from the method that is used to purify residual gas; This residual gas comprises carbon dioxide and oxygen and/or argon; This residual gas is from the equipment that is supplied to the oxygen that contains argon, and this equipment is oxy-fuel combustion equipment, and said device comprises:
-be used to purify the unit of residual gas; This residual gas is made up of the flue gas that leaves boiler; Boiler is used for the oxygen-enriched combusting of fuel by means of the gas that is rich in oxygen and carbon dioxide; Clean unit can be the low temperature purification unit in this case, becomes poor residual fluid so that produce the fluid and the carbon dioxide that are rich in carbon dioxide;
-be used for the unit of preliminary treatment residual fluid, so that obtain to be rich in the stream and the poor stream of carbon dioxide of carbon dioxide; And
-be used for the unit of the poor stream of K cryogenic treatment carbon dioxide, be rich in the part of argon, rich oxygen containing part and argon and/or the poor part of oxygen change so that from the stream of this carbon dioxide poorness, extract.
According to other optional aspect:
-the unit that is used for the poor stream of K cryogenic treatment carbon dioxide comprises at least one interchanger and at least one destilling tower;
-at least one interchanger is a reboiler;
-at least one interchanger is a condenser;
-processing unit makes recyclable part and the rich oxygen containing part that is rich in argon;
-device comprises the device that is used for the oxygen containing part of richness is delivered to boiler and/or pretreatment unit;
-handle also to make the recyclable part that is rich in nitrogen;
-device comprises and is used for a kind of or more kinds of fluid is flowed to the device that is used for the poor stream of K cryogenic treatment carbon dioxide, and this a kind of or more kinds of fluid is from the gas that is used for separation of air and carry the equipment that is used to be supplied oxygen for example to be used for the unit of at least a portion of the oxygen of oxy-fuel combustion;
A kind of in-these fluids is the liquid that is rich in nitrogen, and this liquid that is rich in nitrogen is used to keep the cooling of processing procedure;
A kind of in-these fluids is the gas that is rich in nitrogen, and this gas that is rich in nitrogen will be used as at least one reboiler and/or the recyclegas of at least one condenser of the unit of the poor stream of K cryogenic treatment carbon dioxide;
-pretreatment unit be/comprises carbon dioxide anti-sublimation/distillation unit, and this carbon dioxide anti-sublimation/distillation unit comprises the interchanger of a plurality of parallel connections;
-distillation unit be used to carry the pipeline of rich oxygen containing part to be connected, thereby the mixture of formation carbon dioxide and oxygen and comprises the device that mixture is flowed to fuel oxygen enrichment fuel element alternatively;
-pretreatment unit be/comprises TSA, PSA or VPSA type equipment, and part and carbon dioxide that carbon dioxide is rich in its generation become the poor part that still is rich in argon;
-pretreatment unit be/comprises absorption equipment;
-absorption process is used the aqueous solution of alkaline ph value;
-through injecting NaOH, Na 2CO 3, NH 3Obtain alkaline ph value;
-absorption process is the methanol wash process;
-pretreatment unit be/comprises permeation unit;
-device comprises the device that the stream that is rich in carbon dioxide is circulated to boiler from pretreatment unit.
The oxygen that flows to oxy-fuel combustion equipment by air-separating plant comprises the oxygen of maximum 98mol%, the preferably oxygen of 97mol%, or the oxygen of 96mol% at most at most.
The oxygen that is flowed to equipment, for example oxy-fuel combustion equipment by air-separating plant comprises the argon of 1mol% at least, the argon of 2mol% at least preferably, the perhaps argon of 3mol% at least.
The gas that is rich in argon that is produced by air-separating plant comprises the argon of 50mol% at least, the preferably argon of 70mol%, or the argon of 90mol% at least at least.
Description of drawings
With reference to accompanying drawing the present invention is described in further detail.
Fig. 1 shows oxy-fuel combustion equipment, and it comprises the unit that is used for flue,
Fig. 2 illustrates in greater detail the unit that is used for flue,
Fig. 3 shows and is used at low temperatures flue to remove CO 2The unit,
Fig. 4 shows the device that is used for reclaiming from the residual gas of the unit of Fig. 4 nitrogen and/or oxygen and/or argon, and
Fig. 5 shows the modification of Fig. 4.
The specific embodiment
Fig. 1 is the sketch map of oxy-fuel combustion equipment.Air-separating plant 2 produces oxygen flow 10 and residual nitrogen stream 13, and oxygen flow 10 has the purity of 95mol% usually so that maximize its argon content.This device also produces gaseous nitrogen 13, and is used to handle the not liquid nitrogen 159 of condensables.Oxygen flow 10 is divided into two parts 11 and 12.Main flue gas recirculation stream 15 passes unit 3, and coal 14 is transformed into powder in unit 3.Part 11 is mixed with the circular flow in 3 downstream, unit, and mixture is transported to the combustion chamber of boiler 1.Part 12 is mixed with less important flue gas recirculation stream 16, and it makes burner stable so that temperature is remained on acceptable degree.Water 17 is transported to boiler 1 so that produce steam 18, and steam 18 expands in turbine 8.Be rich in CO 2Flue gas 19---it comprises the CO greater than 70mol% (not calculation of steam) usually 2---experience several processing so that remove impurity.NOx is for example removed through catalytic action in unit 4.Subsequently, dust is removed in unit 5, and subsequent cell 6 is to be used to remove SO 2And/or SO 3Desulphurization system.According to the composition of the product that needs, unit 4 possibly be unnecessary with unit 6.Purification stream 24 from unit 6 (or unit 5, if there is not unit 6) is transferred to compression and clean unit 7, so that the pure relatively CO of generation 2Stream 25 and residual stream 26.
Fig. 2 is the compression of Fig. 1 and the sketch map of clean unit 7.Stream 110 (corresponding to the streams 24 of Fig. 1) get into unit 101, and in unit 101, stream 110 is prepared to the upstream flow of compression unit 102.In unit 101, stream 110 can be cleaned to remove dust, SO 2And/or SO 3, and/or be cooled.
The residual stream 111 that is produced by unit 101 can be condensed water, dust or H 2SO 4, HNO 3, Na 2SO 4, CaSO 4, Na 2CO 3, CaCO 3Or the like.
Compression unit 102 will from the stream 112 of unit 101 from be compressed between 15bar abs (absolute pressure) and 60bar abs near atmospheric pressure, the about high pressure of 30bar abs preferably.Can in comprising intercooled a plurality of step, carry out this compression.In this example, possibly produce condensate 113.The heat of compression can reclaim so that preheat water 17.The stream 114 of heat leaves compression unit 102 and gets into unit 103.This unit 103 makes stream 114 coolings, dry and alternatively it is purified removing mercury, thereby produces residue 115,116 and 117.
Unit 104 is low temperature purification unit.In this example, the minimum temperature in the circulation of " low temperature " expression purified treatment is lower than 0 ℃, and is preferably lower than-20 ℃, perhaps as much as possible near pure CO 2Three phase point/triple point temperature-56.6 ℃.In this unit 104, cooling and condensate flow 118 partly in one or more step.Make one or more be rich in CO 2Stream expand and evaporation so that obtain to be rich in CO 2Product 119.104 reclaim the high-pressure spray 120 of condensables not and flow to pretreatment unit 122 from the unit.Be transferred to processing unit 124 through pretreated stream 123, in processing unit 124, produce a kind of or more kinds of fluid, it can be liquid state and/or gaseous nitrogen 125 and/or liquid state and/or gaseous oxygen 126 and/or gaseous state and/or liquid argon 127.
CO is rich in compression in compression unit 105 2 Product 119.In unit 105, compressed stream 121 is condensed and possibly is pumped.
Fig. 3 shows the low temperature purification device, and this device is equivalent to the unit 104 of Fig. 2.Stream 118 comprises under the pressure that is in about 30bar and the flue gas under the temperature between 15 ℃ and 43 ℃, and stream 118 is filtered in unit 3 so that form stream 5.Stream 118 especially comprises carbon dioxide and NO 2, oxygen, argon and nitrogen.Can under high pressure directly produce stream 118 through unit 103, perhaps flow 118 and can be compressed machine 2 (being shown in broken lines) compression.Stream 5 cooling and partly condensation in exchange pipeline 9.A stream part of 57 is not cooled in exchange pipeline 9, but mixes so that change the temperature of mixture with the remainder of the stream 5 in the downstream of exchange pipeline.The stream of partial condensation is transferred to first phase-splitter 11 and is separated into gas phase 13 and liquid phase 17.Gas phase 13 is divided into two parts so that form stream 15 and stream 21.Stream 21 is used at interchanger 25 tower 43 being seethed with excitement again, and then, stream 21 is transferred to second phase-splitter 22.Stream 15 makes reboiler short circuit (promptly walking around reboiler) so that regulate boiling again.
In valve 19, expand and the flow of liquid 29 of second phase-splitter 22 expands in valve 31 from the liquid 17 of first phase-splitter 11, then, the stream of two expansions is transported to the top of tower 43.Tower 43 is mainly used in and from supply flow 118, removes uncondensable composition (oxygen, nitrogen and argon).
Extract the carbon dioxide stream 33 of poor (poor carbonated) that becomes from the top of tower 43, and flow to compressor 35.The compressive flow 37 that produces with this kind mode is circulated to stream 5.
Extract the stream 67 that is rich in carbon dioxide from the bottom of tower 43, and flow 67 and be divided into two parts.A part 69 so that form stream 85, is flowed 85 by pump 87 pumpings and then from system, remove stream 85 by pump 71 pumpings subsequently.Stream 85 is equivalent to the stream 25 of Fig. 1.The remainder 73 of stream 67 is used for the holding device cooling.
Recommend to purify stream 118 to remove NO 2
NO can separated 2Before or after separate not condensables.
Among Fig. 3, after opening in 69 minutes with stream, the remainder 73 that is rich in the stream of carbon dioxide evaporates in exchange pipeline 9 and is transferred to tower 105 removes NO so that purify 2
This tower can have evaporator overhead condenser and bottom reboiler, and stream 73 is transported to the centre position.In addition, if there is not bottom reboiler, stream 73 is transported to the bottom.
NO 2 Poor stream 79 is extracted out and is turned back to the exchange pipeline 9 from tower 105.This stream 79 is heated, and in compressor 75,77, is compressed, and is transferred to interchanger 65, is drawn out of as stream 78, in interchanger 81,83, is cooled, and mixes with stream 69, thereby form stream 85.Interchanger 81 can be used to heat the water that is ready to use in boiler.Flow 185 cooling exchangers 83 through cold-producing medium, cold-producing medium can be R134a, ammonia, water or the like, and heated cold-producing medium note does 187.Extract from the bottom of tower 105 and to be rich in NO 2Stream 84.This stream 84 is circulated to a position at the upper reaches of filter 3.
In interchanger 55, be cooled and be transferred from the top gas 32 of second phase-splitter 22 to the 3rd phase-splitter 133.Be transferred to tower 43 and remainder (as the stream 45 of medium purity) from the part of the liquid of the 3rd phase-splitter 133 and be divided into two plumes 47,141.Stream 47 evaporation and be transported to the top of tower 43 or 33 mix in interchanger 55 with stream.
Stream 141 expands in valve, in interchanger 55,9, is heated, and in compressor 59, is compressed, and in interchanger 60, is cooled as stream 91 and mixes with compressive flow 5.Be used to make the valve that stream 141 expands to replace with liquid turbine.
Top gas from the 3rd phase-splitter 133 is cooled in heat exchanger 55 (after in compressor 134, being compressed alternatively), and is transferred to the 4th phase-splitter 143.The top gas 157 poor from the carbon dioxide of the 4th phase-splitter 143 is heated in heat exchanger 55, then in interchanger 9, is heated, in interchanger 65, is heated, and as stream 23 with interchanger 63 that compressor 35 connects in expansion.The poor gas 157 of carbon dioxide comprises between carbon dioxide between 30% and 45% and the nitrogen between 30% and 45%.This gas 157 also comprises a large amount of oxygen and argon.Bottom liquid 51 from phase-splitter 143 is transferred to tower 43 with stream 47.
The stream that in turbine 63, expands mixes with the stream that does not pass turbine 115, and in (interchanger) 89, is heated subsequently again.A part 97 that has added hot-fluid expands in turbine 61 and is used as stream 99 and enters atmosphere.
Be rich in not condensables (oxygen and/or argon and/or nitrogen) and comprise CO 2Thereby stream 120 in unit 104, be recovered reclaim stream 120 at least a composition as product.This stream 120 can be from the part of the stream 101 of turbine 61 and/or from the part of the stream 157 in the downstream of the part of the part of the top gas 157 of the 4th phase-splitter 143 at interchanger 55 upper reaches and/or the stream that in turbine 63, expands and/or interchanger 9.
O 2, N 2, Ar, CO 2Molar percentage (example)
Figure BDA0000116138070000091
Table 1
Fig. 4 shows and is used for pretreated device and the device that is used for separating through low temperature distillation convection current 120.This stream 120 at first in pretreatment unit 122 by preliminary treatment.This pretreatment unit is removed in residual gas 120 carbon dioxide of 50mol% at least, and afterwards, K cryogenic treatment produces and is rich in CO 2Stream 169, this stream 169 can 118 be circulated to unit 104 with stream.
Can carry out preliminary treatment through the anti-sublimation/distillation of carbon dioxide in a plurality of parallelly connected interchangers.Alternatively, can carry out preliminary treatment through absorbing (for example passing through methanol wash), absorption, infiltration or several these technology.
For example, under the situation that has oxygen enrichment partly to exist, carry out the distillation of carbon dioxide, thereby form the mixture of the carbon dioxide and the oxygen of the oxygen-enriched combusting that is used for fuel.Through anti-sublimation, the temperature that is processed gas is from-56.6 ℃ of (CO 2Triple point) drop to-170 ℃/-175 ℃, under-170 ℃/-175 ℃, can in air, carry out the low temperature distillation of gas.
In addition, can carry out preliminary treatment, so that produce the part be rich in carbon dioxide and the carbon dioxide poor part that still is rich in argon that becomes through TSA, PSA or VPSA process.
Can carry out preliminary treatment through absorption process, for example use the aqueous solution of alkaline ph value.Alternatively, through injecting NaOH and/or Na 2CO 3And/or NH 3Obtain alkaline ph value.Absorption process also can adopt non-aqueous fluid, for example methyl alcohol.In this example, under pressure, absorb at low temperatures and preferably.
As a kind of alternative, can carry out preliminary treatment through infiltration or through the combination of the various processes mentioned.
Whole carbon dioxide can in pretreatment unit, be removed so that then carry the stream of the carbon dioxide that contains several ppm.This makes can use plate heat exchanger and flange-cooled interchanger device in return.
On the other hand; Still contain carbon dioxide if flow 123, must use reversible interchanger or as the regeneration type interchanger of the 475th page of Springer Verlag " Tieftemperaturtechnik (cryogenic technique) " of publishing, 9.4.2.3 section and the description of 9.4.2.4 section proceed preliminary treatment.Like this, can remove remaining carbon dioxide through the interchanger 130 that passes one of these two types.Clearly, in the porch of tower, supply flow 123 should no longer contain the carbon dioxide that surpasses several ppm.
As shown in Figure 4, after the preliminary treatment, the stream 123 that carbon dioxide becomes poor is transferred to cryogenic distillation unit 124.Stream 123 is cooled to low temperature and is transported to the middle part of the tower 131 with bottom reboiler 133 in interchanger 130.As a kind of alternative, can come cool stream 123 through in turbine, under the situation that produces merit, expand (constant entropy expansion).Gaseous oxygen GOX extracts from top, the bottom of tower 131, in interchanger 130, is heated and is used as product 126 and/or is circulated to pretreatment unit 122 and/or is circulated to boiler 1.Liquid oxygen 136 can extract from the bottom of tower 131, for example extracts as product.The stream 141 that is rich in argon is delivered to tower 137 from tower 131, and impure argon stream 145 condenser 155 belows from tower 137 extract.Bottom liquid stream 143 is back to tower 131.Impure argon 145 is cleaned in denitrification column 139, and denitrification column 139 comprises evaporator overhead condenser 153 and bottom reboiler 151.Bottom in denitrification column 139 produces liquid argon 127.Through injecting the cooling that liquid nitrogen 159 comes holding device, liquid nitrogen 159 is from the air-separating plant 2 of supply oxy-fuel combustion at least in part.Liquid nitrogen 159 is transported to the top of tower 131.This air-separating plant 2 is also carried gaseous nitrogen 13, gaseous nitrogen 13 in interchanger 130, be cooled and heating tower 131 bottom reboiler 133 so that form condensate flow.The part 147 of condensate flow is transported to the evaporator overhead condenser 153 of denitrification column 139 after expansion, a part 165 is transported to the evaporator overhead condenser 155 of tower 137, and a part 157 is transported to the top of tower 131 after expansion.The nitrogen 163 of evaporation mixes with the top gas 135 of tower 131 in condenser 153, in subcooler 160 and interchanger 130, is heated, and forms gaseous nitrogen 165.The nitrogen 161 of evaporation in condenser 155 forms nitrogen stream 161.
At least one tower of device 124 can be contained in the identical ice chest with at least one tower of device 2 alternatively.Therefore, can under the situation that does not need again heating and cooling nitrogen, carry out the transmission of nitrogen 13 and/or 159.For the situation of Fig. 4,, then can omit tower 137,139 if must not reclaim argon.
Fig. 5 shows the modification of the cold part of Fig. 4, in this modification, is transported to the centre position of tower 163 from the cold mixt 123 of interchanger 130, and tower 163 does not have reboiler or evaporator overhead condenser.Top gas 171 from tower 163 constitutes gaseous nitrogen, and bottom liquid 173 is transported to the centre position of tower 165.Gas 175 is back to the bottom of tower 163 from the centre position of tower 165.Tower 165 has bottom reboiler 175 and evaporator overhead condenser 177.Gaseous oxygen 126 and/or liquid oxygen 136 are recovered in the bottom of tower 165, and top liquid 145 is transported to denitrification column 167, form liquid argon 127 in the bottom of denitrification column 167.Denitrification column has bottom reboiler 151 and evaporator overhead condenser 153.
Be transported to the top of tower 163 from the liquid nitrogen 159 of air-separating plant 2.Tower 163 has evaporator overhead condenser, and all reboilers of image pattern 5 are the same with condenser, and this evaporator overhead condenser moves through the circulation from the gaseous nitrogen of air-separating plant 2, and this circulation does not illustrate but the circulation of itself and Fig. 4 is similar.
Alternatively, the conveying of liquid nitrogen 159 can be configured for unique cooling source of processing procedure.
Certainly, it is contemplated that the method for passing through low temperature distillation separated flow 123 except the mode shown in Fig. 4 and Fig. 5.

Claims (17)

1. from residual fluid, produce at least a method that is rich in the fluid and the oxygen containing fluid of at least a richness of argon for one kind; This residual fluid results from the method that is used to purify residual gas; This residual gas comprises carbon dioxide and oxygen and/or argon; This residual gas is from the equipment that is supplied to the oxygen that contains argon, and this equipment is oxy-fuel combustion equipment, and this method may further comprise the steps:
-reclaiming flue gas, said flue gas results from fuel in the combustion chamber of boiler (1) by means of being rich in oxygen and carbon dioxide and containing the oxygen-enriched combusting of the gas of argon;
-purify the residual gas that constitutes by the flue gas that leaves boiler through the low temperature purification method, so that the fluid (119) of carbon dioxide and the residual fluid (120) that carbon dioxide becomes poor are rich in generation;
The residual fluid that the said carbon dioxide of-preliminary treatment becomes poor is so that obtain to be rich in the stream (169) and the poor stream (123) of carbon dioxide of carbon dioxide;
The stream that the said carbon dioxide of-K cryogenic treatment is poor is so that extract at least one part (127) that is rich in argon and the become part (125) of poorness of at least one rich oxygen containing part (126) and at least one argon and/or oxygen from this stream.
2. according to the method for claim 1; It is characterized in that; The poor stream of the said carbon dioxide of K cryogenic treatment is included at least one interchanger (130), the step of in reversible or regeneration type interchanger, cooling off in condenser, alternatively in reboiler, alternatively alternatively and the step of in destilling tower (131,163), distilling.
3. according to each method in the aforementioned claim, it is characterized in that, in air-separating plant (2), preferably pass through separating air by cryogenic distillation; So that produce rich oxygen containing stream (10); The oxygen containing stream of said richness (10) comprises maximum 99% oxygen, preferably comprises maximum 98% oxygen or the oxygen of 97mol% at most, and the oxygen containing stream of said richness (10) also comprises argon; Preferably comprise the argon of 2mol% at least or the argon of 3mol% at least, and should be transferred to be used for oxy-fuel combustion by the oxygen containing stream of richness.
5. according to each method in the aforementioned claim, it is characterized in that the oxygen containing part of said richness (126) is used for the oxygen-enriched combusting of fuel and/or is used for the preliminary treatment of the residual gas that carbon dioxide becomes poor.
6. according to each method in the aforementioned claim, it is characterized in that said processing also makes the recyclable part (125) that is rich in nitrogen.
7. according to each method in the aforementioned claim; It is characterized in that; In the process of handling the poor stream of carbon dioxide, use from being used for from the unit (2) of air divided gas flow or being used for one or more fluids of unit of the gas of separation of air; Said unit is carried and is used to be supplied the equipment of oxygen, for example is used at least a portion of the oxygen of oxy-fuel combustion; In this case, said being used for can be accommodated in the single ice chest from least one tower of the unit of air divided gas flow and at least one tower of said processing unit.
8. according to the method for claim 7, it is characterized in that a kind of in these fluids is the liquid (159) that is rich in nitrogen, this liquid that is rich in nitrogen keeps the cooling of the low-temperature process of the poor stream of carbon dioxide at least in part.
9. according to the method for claim 7 or 8, it is characterized in that a kind of in these streams is the gas (13) that is rich in nitrogen, this gas that is rich in nitrogen is as at least one reboiler of K cryogenic treatment and/or the recyclegas of at least one condenser.
10. according to each method in the aforementioned claim, it is characterized in that before K cryogenic treatment, the carbon dioxide of the 50mol% at least in the residual gas is removed in preliminary treatment.
11. the method according to claim 10 is characterized in that, carries out preliminary treatment through the anti-sublimation/distillation of carbon dioxide in a plurality of parallelly connected interchangers at least in part.
12. the method according to claim 11 is characterized in that, under the situation that has oxygen enrichment partly to exist, carries out the distillation of carbon dioxide, thereby forms the oxygen-enriched combusting of carbon dioxide/oxygen mixture for use in fuel.
13. the method according to claim 10 or 11 or 12 is characterized in that, carries out preliminary treatment through TSA, PSA or VPSA process at least in part, so that produce the part be rich in carbon dioxide and the carbon dioxide poor part that still is rich in argon that becomes.
14. the method according to claim 10 or 11 or 12 or 13 is characterized in that, at least in part through absorption process, through using methanol wash, carries out preliminary treatment alternatively.
15. according to each method among the claim 10-14, it is characterized in that, carry out preliminary treatment through infiltration at least in part.
16., it is characterized in that the stream that is rich in carbon dioxide (169) that is produced by preliminary treatment is circulated to the equipment of oxygen consumed, preferably is circulated to the oxy-fuel combustion boiler, preferably is circulated to the combustion chamber according to each method in the aforementioned claim.
17. from residual fluid, produce at least a fluid of argon and the device of the oxygen containing fluid of at least a richness of being rich in for one kind; This residual fluid results from the method that is used to purify residual gas; This residual gas comprises carbon dioxide and oxygen and/or argon; This residual gas is from the equipment that is supplied to the oxygen that contains argon, and this equipment is oxy-fuel combustion equipment, and said device comprises:
-be used to purify residual gas, particularly leave the flue gas of boiler; So that the fluid of carbon dioxide and the unit (104) of the residual fluid that carbon dioxide becomes poor are rich in generation; Said boiler is used for the oxygen-enriched combusting of fuel by means of the gas that is rich in oxygen and carbon dioxide, and wherein clean unit can be the low temperature purification unit;
-be used for the said residual fluid of preliminary treatment, so that obtain to be rich in the stream of carbon dioxide and the unit (122) of the stream of carbon dioxide poorness; And
-be used for the poor stream of the said carbon dioxide of K cryogenic treatment, so that from the poor stream of this carbon dioxide, extract the unit (124) that is rich in the part that the part of argon, rich oxygen containing part and argon and/or oxygen becomes poor.
18. the device according to claim 17 is characterized in that, the said unit that is used for the poor stream of K cryogenic treatment carbon dioxide comprises at least one interchanger (130) and at least one destilling tower (131,139,163,165,167).
CN2010800247790A 2009-06-03 2010-05-28 Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid Pending CN102695935A (en)

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FR0953648A FR2946417A1 (en) 2009-06-03 2009-06-03 METHOD AND APPARATUS FOR PRODUCING AT LEAST ONE ARGON-ENRICHED FLUID AND / OR AT LEAST ONE OXYGEN-ENRICHED FLUID FROM A RESIDUAL FLUID
FR0953648 2009-06-03
PCT/FR2010/051031 WO2010139884A2 (en) 2009-06-03 2010-05-28 Method and apparatus for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a residual fluid

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