CN101216175A - Oxygen carrier gasifying combustion method for loading oxygen and device - Google Patents
Oxygen carrier gasifying combustion method for loading oxygen and device Download PDFInfo
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- CN101216175A CN101216175A CNA200710190246XA CN200710190246A CN101216175A CN 101216175 A CN101216175 A CN 101216175A CN A200710190246X A CNA200710190246X A CN A200710190246XA CN 200710190246 A CN200710190246 A CN 200710190246A CN 101216175 A CN101216175 A CN 101216175A
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Abstract
The invention discloses an oxygen carrying gasification combustion method with an oxygen carrier as well as relevant apparatus; the method is characterized in that the oxygen carrier is arranged inside an air reactor fluidized bed; if fluidized air is fed, oxysome reacts with oxygen in the air before high-value metal oxide is heated to obtain; then, the oxide will be separated through a two-stage separator; the high-temperature oxygen denuded air, which is separated, is exhausted out of the upper-end of the separator; the separated oxygen carrier goes through a returning dipleg to enter a mixing and gasification chamber; in a circulation fluidized bed in the air reactor, an oxygen carrying reaction happens between the oxygen carrier and oxygen in the air: The oxygen carrier from the reaction flows into the dipleg after being separated by the two-stage separator, so that the oxygen carrier and the fuel can together enter the gasification chamber below the fuel reactor fluidized bed; in the gasification chamber, a gasification reaction happens to the fuel and the water vapour, so as to create a synthetic gas. Meanwhile, the oxygen carrier releases oxygen and a reduction reaction happens with a synthetic gas or a fuel, before carbon dioxide is gained.
Description
Technical field
The present invention relates to a kind of process of utilizing oxygen carrier coal/natural coal/petroleum coke to be similar to steam gasification and pure oxygen burning, realize carrying out in the combustion process method and apparatus of carbon dioxide separation, relate in particular to a kind of oxygen carrier gasifying combustion method for loading oxygen and device thereof.
Background technology
One of sustainable development strategies of using energy source realizes the high-efficiency cleaning utilization of the energy.Coal, natural coal and petroleum coke etc. in combustion process, reduce emission of carbon-dioxide as the energy, realize that the high-efficiency cleaning utilization is the Future Development direction.Conventional air directly burns, and except generating with nitrogen oxide, the carbon dioxide eliminating consumed energy is big in the flue gas; By the method that coal gasification is carried out carbon dioxide separation and burning again, also need to consume the energy consumption of system oxygen and separating carbon dioxide.The method is as being used for generating, and the energy of consumption can account for station service power consumption rate more than 10%, has a strong impact on energy utilization efficiency.
Summary of the invention
The invention provides and a kind ofly can separate oxygen carrier gasifying combustion method for loading oxygen and the device thereof that obtains carbon dioxide, effective separating carbon dioxide when by the present invention coal/natural coal/petroleum coke being carried out power conversion has the advantage that need not consume extra energy consumption and be beneficial to environmental protection.
Method and technology scheme of the present invention is as follows:
A kind of oxygen carrier gasifying combustion method for loading oxygen, to place in the air reactor fluid bed as the lower valency metal oxide or the metal simple-substance of oxygen carrier, feed fluidization air from the lower end of air reactor fluid bed, obtain the high valence state metal oxide that heated up behind lower valency metal oxide or metal simple-substance oxygen carrier and the airborne oxygen reaction, it is separated through the two-stage separator; High temperature oxygen denuded air after the separation is discharged from the upper end of separator, and the oxygen carrier after the separation through the returning charge leg, enters the mixing gasifying chamber, bottom of fuel reaction device fluid bed; The lower end of fuel reaction device fluid bed feeds gasifying medium steam, in the mixing gasifying chamber, the heat of coal, natural coal or petroleum coke and steam gasification is provided by oxygen carrier, synthesis gas after the gasification and oxygen carrier generation reduction reaction, the metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, fully reaction in the riser of fuel reaction device fluid bed top, enter separator then, clean carbon dioxide steam gaseous mixture after the separation is discharged from this separator upper end, obtains pure carbon dioxide after the water outlet of condensing; Oxygen carrier after the separation and carbon residue hybrid solid thing enter the air reactor fluid bed through oxygen carrier circulation dipleg, with oxygen carrier regeneration, realize oxygen carrier.
Device technique scheme of the present invention is as follows:
A kind of device that is used to implement the described oxygen carrier method of claim 1, by the air reactor fluid bed, oxygen carrier heat-carrying refeed line, the oxygen carrier regeneration separators, oxygen carrier regeneration refeed line and fuel reaction device fluid bed are formed, the upper end of air reactor fluid bed is connected with the oxygen denuded air separator, oxygen denuded air separator lower end discharge gate links to each other with an end of oxygen carrier heat-carrying refeed line, the other end of oxygen carrier heat-carrying refeed line links to each other with the lower end of fuel reaction device fluid bed, the upper end of fuel reaction device fluid bed links to each other with the upper end of oxygen carrier regeneration separators, oxygen carrier regeneration separators lower end links to each other with an end of oxygen carrier regeneration refeed line, and the other end of oxygen carrier regeneration refeed line links to each other with the bottom of air reactor fluid bed.
Compared with prior art, the present invention has following advantage:
(1) in the air reactor recirculating fluidized bed, oxygen carrier (as: lower valency iron oxide, nickel, copper, zinc etc.) is planted the oxygen reaction with airborne oxygen:
2Ni+O
2→ 2NiO+ heat release
2Fe
xO
y+ O
2→ 2Fe
xO
Y+1+ heat release
2Cu+O
2→ 2CuO+ heat release
2Zn+O
2→ 2ZnO+ heat release
The oxygen carrier (as: high valence state iron oxide, nickel oxide, cupric oxide, zinc oxide etc.) that reaction generates after the two-stage separator separates, enters dipleg, with fuel, enter fuel reaction device fluid bed bottom vaporizer, at vaporizer, fuel and the reaction of steam generating gasification generate synthesis gas.Oxygen carrier (is reduced to Me simultaneously
xO
y) discharge oxygen, with synthesis gas or fuel generation reduction reaction, generate carbon dioxide:
H
2O+C → 4H
2+ CO+ heat absorption
Me
xO
Y+1+ CO → CO
2+ Me
xO
y+ heat absorption
Me
xO
Y+1+ H
2→ H
2O+Me
xO
y+ heat absorption
2Me
xO
Y+1+ C → CO
2+ 2Me
xO
y+ heat absorption
The flue gas that produces through two groups of cyclone separators, is discharged flue gas, and flue gas reclaims condensation through energy and is pure carbon dioxide, and separator will be isolated solid material and be divided into two strands.Wherein one solid material enters the air reactor fluid bed through dipleg, carries out the oxidation regeneration reaction, finishes the oxygen carrier regenerative process; Another strand enters fuel reaction device fluid bed, gasifies and reduction reaction, improves the conversion ratio of carbon.
(2) the present invention has adopted two groups of smoke separators, the solid material of fuel reaction device fluid bed separator can be divided into two strands, by connecting pipe, solid material is sent into air reactor fluid bed and fuel reaction device fluid bed respectively.Air reactor fluid bed running temperature can be controlled in about 800 ℃~1250 ℃, and after-heat can be by laying heating surface or strengthening air mass flow and controlled; Fuel reaction device fluid bed bottom mixing gasifying room temperature is controlled at about 800 ℃~1200 ℃, and the top riser temperature can be hanged down slightly in 500 ℃~900 ℃ scopes and be moved.
(3) the present invention by metal oxide as oxygen carrier, with steam, coal/natural coal/petroleum coke under 900 ℃~1250 ℃ condition, gasify and burning, has identical smoke components (promptly obtaining the flue gas of a carbonated and steam) with adopting the pure oxygen burning mode, but the energy consumption that need not to produce pure oxygen is (usually for generating, its system oxygen energy consumption accounts for station service more than 10%), and not having NOx to generate, external discharging can be controlled effectively in the conversion process of energy.
Description of drawings
Fig. 1 is an embodiment of the invention structural representation, and H is the oxygen denuded air outlet among the figure, and I1 and I2 are the carbon dioxide steam outlet, and B is for replenishing the oxygen carrier inlet, and F is a fuel inlet.
Fig. 2 is a kind of scheme of utilizing of the embodiment of the invention.
The specific embodiment
A kind of oxygen carrier gasifying combustion method for loading oxygen will place in the air reactor fluid bed as the lower valency metal oxide or the metal simple-substance of oxygen carrier, is Fe as the metal oxide of oxygen carrier
2O
3, FeO, Fe
3O
4, CuO, Cu
2O, NiO, ZnO are Fe, Cu, Zn, Ni as the metal simple-substance of oxygen carrier.Feed fluidization air from the lower end C of air reactor fluid bed then, obtain the high valence state metal oxide that heated up behind lower valency metal oxide or metal simple-substance oxygen carrier and the airborne oxygen reaction, it is separated through the two-stage separator; High temperature oxygen denuded air after the separation is discharged from the upper end H of separator, and the oxygen carrier after the separation through the returning charge leg, enters the mixing gasifying chamber, bottom of fuel reaction device fluid bed; The lower end E of fuel reaction device fluid bed feeds gasifying medium steam, in the mixing gasifying chamber, the heat of coal, natural coal or petroleum coke and steam gasification is provided by oxygen carrier, synthesis gas after the gasification and oxygen carrier generation reduction reaction, the metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, fully reaction in the riser of fuel reaction device fluid bed top, enter separator then, clean carbon dioxide steam gaseous mixture after the separation is discharged from this separator upper end I1, obtains pure carbon dioxide after the water outlet of condensing; Oxygen carrier after the separation and carbon residue hybrid solid thing enter the air reactor fluid bed through oxygen carrier circulation dipleg 4, with oxygen carrier regeneration, realize oxygen carrier.
The metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, after in the riser of fuel reaction device fluid bed top, fully reacting, part enters another separator, clean carbon dioxide steam gaseous mixture after the separation is discharged from this separator upper end I2, oxygen carrier after this separator separates and carbon residue hybrid solid thing are through carbon residue circulation dipleg 5-4, return the gasification reactor chamber that enters fuel reaction device fluid bed bottom again, improve the carbon burnout rate.
Further describe in detail below: will place in the air reactor fluid bed as the lower valency metal oxide or the metal simple-substance of oxygen carrier, feed fluidization air from the bottom of air reactor fluid bed, air reactor fluid bed running temperature can be controlled in about 800 ℃~1250 ℃, at this moment, obtain high valence state metal oxide behind lower valency metal oxide or metal simple-substance oxygen carrier and the airborne oxygen reaction, make through the two-stage separator, the clean oxygen debt air of the high temperature after the separation can do work and generate electricity or UTILIZATION OF VESIDUAL HEAT IN again; Oxygen carrier after the separation through the returning charge leg, enters the mixing gasifying chamber, bottom of fuel reaction device fluid bed, and the high temperature oxygen carrier provides the heat of coal/natural coal/petroleum coke and steam gasification, and the mixing gasifying room temperature is controlled at about 800 ℃~1200 ℃; At this moment, coal/natural coal/petroleum coke and the reaction of steam generating gasification, synthesis gas after the gasification and oxygen carrier can be in vaporizer generation reduction reactions, the metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, fully reaction in the fluid bed riser, riser temperature can be hanged down slightly in 500 ℃~900 ℃ scopes and be moved; After this, flue gas enters two groups of two-stage separators, and the clean carbon dioxide steam gaseous mixture after the separation through acting generating or UTILIZATION OF VESIDUAL HEAT IN, obtains pure carbon dioxide after the water outlet of condensing; Wherein a component from after oxygen carrier (contain unreacted intact carbon residue) through dipleg, return the gasification reactor chamber that enters fuel reaction device fluid bed bottom again, improve the carbon burnout rate; Another component from after oxygen carrier enter the air reactor fluid bed through dipleg, with oxygen carrier regeneration, realize oxygen carrier.Fuel reaction device fluid bed internal reaction product lower valency metal oxide or metal simple-substance, by two groups of fuel reaction device fluid bed separators, lower valency metal oxide or metal simple-substance oxygen carrier are divided into two strands, wherein one is gone back ortho states oxygen carrier (contain unreacted intact carbon residue) and returns through dipleg and enter fuel reaction device fluid bed bottom vaporizer, further improve the conversion ratio of carbon, improve burnout rate; Another thigh is gone back ortho states oxygen carrier (containing the intact carbon residue of unreacted) and is entered the air reactor fluid bed through dipleg, to go back the ortho states oxygen carrier oxidating is the oxidation state oxygen carrier, and raising temperature, through air reactor fluid bed separator, be re-used as the vaporizer that the oxygen carrier thermophore enters into fuel reaction device fluid bed bottom.
Embodiment
A kind of device that is used to implement described oxygen carrier method, by air reactor fluid bed 1, oxygen carrier heat-carrying refeed line 2, oxygen carrier regeneration separators 3, oxygen carrier regeneration refeed line 4 and fuel reaction device fluid bed 5 are formed, the upper end of air reactor fluid bed 1 is connected with oxygen denuded air separator 1-1, oxygen denuded air separator 1-1 lower end discharge gate links to each other with an end of oxygen carrier heat-carrying refeed line 2, the other end of oxygen carrier heat-carrying refeed line 2 links to each other with the lower end of fuel reaction device fluid bed 5, the upper end of fuel reaction device fluid bed 5 links to each other with the upper end of oxygen carrier regeneration separators 3, oxygen carrier regeneration separators 3 lower ends link to each other with an end of oxygen carrier regeneration refeed line 4, and the other end of oxygen carrier regeneration refeed line 4 links to each other with the bottom of air reactor fluid bed 1.Be provided with oxygen carrier in the lower end of air reactor recirculating fluidized bed 1 and replenish a mouthful B.Fuel reaction device recirculating fluidized bed 5 is formed by promoting tubular type, mixing gasifying reative cell 5-3 and changeover portion 5-2, promotes tubular type and is connected with mixing gasifying reative cell 5-3 by changeover portion 5-2.The top outlet of one-level oxygen denuded air separator 1-1 is communicated with secondary oxygen denuded air separator 1-2, secondary oxygen denuded air separator 1-2 establishes the upper end oxygen denuded air outlet H, one-level oxygen denuded air separator 1-1 lower end is connected with oxygen carrier returning charge leg 1-3, the bottom of secondary oxygen denuded air separator 1-2 and oxygen carrier returning charge leg 1-3 communicate, the lower end of oxygen carrier returning charge leg 1-3 is connected with moving bed 1-4, moving bed 1-4 lower end is provided with fluidized wind import A, and moving bed 1-4 bottom is provided with material outlet and the lower end discharge gate of this material outlet as oxygen denuded air separator 1-1 used.Upper end at fuel reaction device fluid bed 5 also is connected with the carbon residue separator, this carbon residue separator is by one-level flue gas carbon residue separator 5-1 and secondary smoke carbon residue separator 5-5, one-level flue gas carbon residue separator 5-1 lower end is connected with carbon residue returning charge leg 5-6, carbon residue returning charge leg 5-6 and secondary smoke carbon residue separator 5-5 outlet communicate, carbon residue returning charge leg 5-6 lower end links to each other with moving bed 5-7, moving bed 5-7 lower end is provided with fluidized wind import G, moving bed 5-7 bottom is provided with material outlet, is communicated with the bottom of reactor fluidisation bed 5 by circulation refeed line 5-4.Oxygen carrier regeneration separators 3 is made up of one-level flue gas oxygen carrier regeneration separators 3-1 and secondary smoke oxygen carrier regeneration separators 3-2, one-level flue gas oxygen carrier regeneration separators 3-1 and secondary smoke oxygen carrier regeneration separators 3-2 outlet communicate, the outlet of one-level flue gas oxygen carrier regeneration separators 3-1 is connected with oxygen carrier regeneration returning charge leg, the lower end of oxygen carrier regeneration returning charge leg 3 is connected with moving bed 3-3, moving bed 3-3 lower end is provided with fluidized wind import D, and moving bed 3-3 bottom is provided with material outlet and this material outlet links to each other with an end of oxygen carrier regeneration refeed line 4.
A kind of the present invention of utilization is implemented in the method for carrying out carbon dioxide separation in coal/natural coal/petroleum coke combustion process, carries out the cleaning generating with coal/natural coal/petroleum coke that is:, realizes the separation of carbon dioxide simultaneously.With reference to Fig. 2, after air compresses through compressor 8, become pressure-air, enter the air reactor fluid bed of embodiment 1, through with go back ortho states oxygen carrier reaction, obtain the HTHP oxygen denuded air and separate through air reactor oxygen carrier separator, the high pressure oxygen denuded air enters turbine 7 acting of expanding, drive generator 6 generatings, turbine 7 exhausts enter waste heat recovery generating system 9 again and produce electric power or steam.The oxygen carrier that separates through air reactor oxygen carrier separator enters fuel reaction device fluid bed, with waste heat recovery generating system 9 or the 12 steam E that produce and coal/natural coal/petroleum coke F gasification and burning, generate high-temperature flue gas, high-temperature flue gas requires to separate through two groups of fuel reaction device separators, flue gas expands through turbine 10 and does work, drive generator 11 generatings, turbine 10 exhausts enter waste heat recovery generating system 12 again and produce electric power or steam, and waste heat recovery generating system 12 tail gas K are pure carbon dioxide through condensation.The oxygen carrier that separates through fuel reaction device separator is divided into two strands, and one returns fuel reaction device fluid bed, participates in gasification and combustion reaction, and another strand enters the oxygen carrier that the air reactor fluid bed is realized oxygen carrier.
Claims (9)
1. oxygen carrier gasifying combustion method for loading oxygen, it is characterized in that and to place in the air reactor fluid bed as the lower valency metal oxide or the metal simple-substance of oxygen carrier, feed fluidization air from the lower end (C) of air reactor fluid bed, obtain the high valence state metal oxide that heated up behind lower valency metal oxide or metal simple-substance oxygen carrier and the airborne oxygen reaction, it is separated through the two-stage separator; High temperature oxygen denuded air after the separation is discharged from the upper end (H) of separator, and the oxygen carrier after the separation through the returning charge leg, enters the mixing gasifying chamber, bottom of fuel reaction device fluid bed; The lower end (E) of fuel reaction device fluid bed feeds gasifying medium steam, in the mixing gasifying chamber, the heat of coal, natural coal or petroleum coke and steam gasification is provided by oxygen carrier, synthesis gas after the gasification and oxygen carrier generation reduction reaction, the metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, fully reaction in the riser of fuel reaction device fluid bed top, enter separator then, clean carbon dioxide steam gaseous mixture after the separation is discharged from this separator upper end (I1), obtains pure carbon dioxide after the water outlet of condensing; Oxygen carrier after the separation and carbon residue hybrid solid thing enter the air reactor fluid bed through the oxygen carrier dipleg (4) that circulates, and with oxygen carrier regeneration, realize oxygen carrier.
2. oxygen carrier gasifying combustion method for loading oxygen according to claim 1 is characterized in that the metal oxide as oxygen carrier is Fe
2O
3, FeO, Fe
3O
4, CuO, Cu
2O, NiO, ZnO are Fe, Cu, Zn, Ni as the metal simple-substance of oxygen carrier.
3. oxygen carrier method according to claim 1, it is characterized in that the metal oxide of high valence state is reduced to the metal oxide or the metal simple-substance of lower valency, after in the riser of fuel reaction device fluid bed top, fully reacting, part enters another separator, clean carbon dioxide steam gaseous mixture after the separation is discharged from this separator upper end (J2), oxygen carrier after this separator separates and carbon residue hybrid solid thing are through carbon residue circulation dipleg (5-4), return the gasification reactor chamber that enters fuel reaction device fluid bed bottom again, improve the carbon burnout rate.
4. device that is used to implement the described oxygen carrier method of claim 1, it is characterized in that by air reactor fluid bed (1), oxygen carrier heat-carrying refeed line (2), oxygen carrier regeneration separators (3), oxygen carrier regeneration refeed line (4) and fuel reaction device fluid bed (5) are formed, the upper end of air reactor fluid bed (1) is connected with oxygen denuded air separator (1-1), oxygen denuded air separator (1-1) lower end discharge gate links to each other with an end of oxygen carrier heat-carrying refeed line (2), the other end of oxygen carrier heat-carrying refeed line (2) links to each other with the lower end of fuel reaction device fluid bed (5), the upper end of fuel reaction device fluid bed (5) links to each other with the upper end of oxygen carrier regeneration separators (3), oxygen carrier regeneration separators (3) lower end links to each other with an end of oxygen carrier regeneration refeed line (4), and the other end of oxygen carrier regeneration refeed line (4) links to each other with the bottom of air reactor fluid bed (1).
5. device according to claim 4 is characterized in that being provided with oxygen carrier in the lower end of air reactor recirculating fluidized bed (1) replenishes mouthful (B).
6. device according to claim 4, it is characterized in that forming by promoting tubular type, mixing gasifying reative cell (5-3) and changeover portion (5-2), promote tubular type and be connected with mixing gasifying reative cell (5-3) by changeover portion (5-2) at fuel reaction device recirculating fluidized bed (5).
7. device according to claim 4, the top outlet that it is characterized in that one-level oxygen denuded air separator (1-1) is communicated with secondary oxygen denuded air separator (1-2), oxygen denuded air outlet (H) is established in secondary oxygen denuded air separator (1-2) upper end, one-level oxygen denuded air separator (1-1) lower end is connected with oxygen carrier returning charge leg (1-3), the bottom of secondary oxygen denuded air separator (1-2) and oxygen carrier returning charge leg (1-3) communicate, the lower end of oxygen carrier returning charge leg (1-3) is connected with moving bed (1-4), moving bed (1-4) lower end is provided with fluidized wind import (A), and moving bed (1-4) bottom is provided with material outlet and the lower end discharge gate of this material outlet as oxygen denuded air separator (1-1) used.
8. device according to claim 4, it is characterized in that also being connected with the carbon residue separator in the upper end of fuel reaction device fluid bed (5), this carbon residue separator is by one-level flue gas carbon residue separator (5-1) and secondary smoke carbon residue separator (5-5), one-level flue gas carbon residue separator (5-1) lower end is connected with carbon residue returning charge leg (5-6), carbon residue returning charge leg (5-6) and secondary smoke carbon residue separator (5-5) outlet communicate, carbon residue returning charge leg (5-6) lower end links to each other with moving bed (5-7), moving bed (5-7) lower end is provided with fluidized wind import (G), moving bed (5-7) bottom is provided with material outlet, is communicated with by the bottom of circulation refeed line (5-4) with reactor fluidisation bed (5).
9. device according to claim 4, it is characterized in that oxygen carrier regeneration separators (3) is made up of one-level flue gas oxygen carrier regeneration separators (3-1) and secondary smoke oxygen carrier regeneration separators (3-2), one-level flue gas oxygen carrier regeneration separators (3-1) and secondary smoke oxygen carrier regeneration separators (3-2) outlet communicate, the outlet of one-level flue gas oxygen carrier regeneration separators (3-1) is connected with oxygen carrier regeneration returning charge leg, the lower end of oxygen carrier regeneration returning charge leg (3) is connected with moving bed (3-3), moving bed (3-3) lower end is provided with fluidized wind import (D), and moving bed (3-3) bottom is provided with material outlet and this material outlet links to each other with an end of oxygen carrier regeneration refeed line (4).
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CN200710190246XA CN101216175B (en) | 2007-11-23 | 2007-11-23 | Oxygen carrier gasifying combustion method for loading oxygen and device |
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