CN1840965A - Oxy-fuel combustion process - Google Patents
Oxy-fuel combustion process Download PDFInfo
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- CN1840965A CN1840965A CNA2006100741199A CN200610074119A CN1840965A CN 1840965 A CN1840965 A CN 1840965A CN A2006100741199 A CNA2006100741199 A CN A2006100741199A CN 200610074119 A CN200610074119 A CN 200610074119A CN 1840965 A CN1840965 A CN 1840965A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D14/00—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
- F23D14/32—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid using a mixture of gaseous fuel and pure oxygen or oxygen-enriched air
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C1/00—Combustion apparatus specially adapted for combustion of two or more kinds of fuel simultaneously or alternately, at least one kind of fuel being either a fluid fuel or a solid fuel suspended in a carrier gas or air
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
Production of oxygen-enriched gas streams is disclosed herein. Air streams contact an oxygen-selective mixed conductor particularly a perovskite material whereby oxygen is retained or adsorbed on the perovskite and can be employed in a variety of processes such as in combusting a fuel gas, heat recovery and boiler related operations.
Description
The application requires the U.S. Patent application 10/313 of submission on December 6th, 2002,876 priority, thick pool has required the interim U.S. Patent application 60/346 of submission on January 8th, 2002,582,60/346 of submission on January 8th, 2002,60/347,268 the priority of submitting on January 10th, 597 and 2002.
Background of invention
The main purpose of combustion process is to produce heat.In power plant or industrial boiler system, utilize this heat to produce high-pressure steam, and then can be used to carry out the technology heating or be used for generating.The most conventional combustion process utilizes air to originate as oxygen.The nitrogen that exists in the air can not make combustion process be benefited, even may throw into question.For example, nitrogen may react with oxygen under ignition temperature, forms nitrogen oxide (NOx), and this is bad pollutant.In many cases, must handle combustion product, the discharging of nitrogen oxide is reduced to environment can be accepted below the limit.And the existence of nitrogen has increased the volume of flue gas, this and then the thermal efficiency that increases thermal loss and reduce combustion process.In addition, nitrogen content height may make it be difficult to catch CO as product in the fuel gas
2Or the usefulness of confession separation.At the current CO that emphasizes
2Under the situation of separation with the ill-effect that alleviates global warming, exploitation is caught CO in cost-effective mode
2Method be very important.
A kind of method of eliminating nitrogen from burning effluent or fuel gas is to replace air with purity oxygen in combustion process.Yet, with oxygen burning takes place and can produce very high temperature, thereby the part of the necessary recycling flue gas that produces is to relax temperature.This so oxygen content is diluted to about 27% (remaining is about 73% CO
2And water), and with flame temperature be maintained to identical value.Though this scheme can be eliminated the problem that nitrogen brings, the cost of oxygen is too high in this case, can not make it have economically attraction.
U.S. Patent number 5,888 has been discussed with the ion transfer ceramic membrane in 272 and has been produced rich oxygen containing air-flow, this patent disclosure feed stream is divided into rich oxygen containing air-flow that is used for the combustion chamber and the method that lacks the air-flow of oxygen.Feed stream is after overcompression, with comprising that having the ion transfer module that keeps object plane and the ion transport membranes that permeates object plane isolates oxygen from the feed stream of compression.Infiltration object plane with at least a portion flushing ion transport membranes of the combustion product air-flow that from the gas stream burning chamber of the infiltration object plane that leaves the ion transfer module, obtains.The shortcoming of this oxygen production method is the difficulty of making the cost height of film and producing the leakproof film structure.Usually, oxygen recovery rate is also lower in film unit.
The oxygen selectivity ceramic material production that the present invention is based on and adopt high temperature, makes particle form is applicable to the Oxygen Flow of the nonnitrogenous substantially gas that oxygen-fuel is used, and a kind of attractive selection that reduces the oxygen cost can be provided.This system adopts pressure oscillation or temperature change pattern, because the oxygen reserve capacity of ceramic material depends on temperature and pressure strongly.This method produces several advantages usually at the temperature operation that is higher than 300 ℃, comprises that oxygen capacity is big and the oxygen selectivity is big.The key advantage of this method is the oxygen selective material that it adopts conventional pellet shaped formula in the fixed bed reactors, and available conventional method is made this material.Therefore, compare with the above-mentioned film based method of the special manufacturing of needs, sealing and number of assembling steps, this method can more easily be used for commercial use, and knownly has several problems aspect this.Another advantage of fixed bed ceramic base system is the oxygen flow that it can directly produce nonnitrogenous substantially gas, and its oxygen concentration is suitable for oxygen-fuel and uses.It produces high purity oxygen gas earlier unlike conventional method as cryogenic air separation process, dilution obtains required oxygen concentration then.
The objective of the invention is to be applicable to that by production the oxygen flow of the nonnitrogenous substantially gas of oxygen expenditure technology reduces the oxygen cost.It relates to the oxygen flow that uses oxygenous high-temperature systems to produce nonnitrogenous substantially gas.More specifically say, it described oxygen selectivity ceramic material from air draught oxygen separation producing in oxygen expenditure technology, as can be used as the purposes in the oxygen flow that the oxygen that replaces air originates in Industrial Boiler or the fired heater.
Brief summary of the invention
The present invention relates to be formed for the method for the product gas flow of oxygen expenditure technology, this method may further comprise the steps circularly:
A) with air input by containing the reactor of oxygen selectivity mixed conductor material, on oxygen selectivity mixed conductor material, keep oxygen thus, reactor is being higher than under 300 ℃ the temperature; With
B) the air-flow input that will lack oxygen discharges oxygen from oxygen selectivity mixed conductor material thus by this reactor.
Oxygen selectivity mixed conductor material is that structural formula is A
1-XM
XBO
3-δPerovskite type ceramic, wherein A is a rare earth element ion, M is Sr, Ca, Ba, V or its mixture; B is Co, Mn, Cr, Fe or its mixture; X is from greater than 0 to about 1; δ is the deviation that replaces the coatings of stoichiometric composition that rare earth element ion produces owing to Sr, Ca and Ba.X preferably is about 0.1-1, is most preferably 0.2-1, and A is La, Y or its mixture; M is Sr, Ca or its mixture; B is Co, Fe or its mixture.
One or more reactors of available existence are implemented this method.With air and two strands of air-flows lacking oxygen with and the mode of stream or adverse current be input in the reactor.
During the oxygen of this method keeps step (a), produced the gas that is rich in nitrogen as accessory substance, during step (b), produced the oxygen flow of nonnitrogenous substantially gas.The oxygen flow of nonnitrogenous substantially gas is used for oxygen expenditure technology.This oxygen expenditure technology is selected from chemical oxidation process, partial oxidation technology, boiler, burning process and gasifying process etc.
In another embodiment of the invention, the method for operation oxygen expenditure technology is disclosed, this method may further comprise the steps in succession:
A) with air input by containing the reactor of oxygen selectivity mixed conductor material, on oxygen selectivity mixed conductor material, keep oxygen thus, reactor is being higher than under 300 ℃ the temperature; With
B) will lack the product gas input reactor of oxygen from least a portion of oxygen expenditure technology, thereby form the oxygen flow of nonnitrogenous substantially gas; With
C) oxygen flow with nonnitrogenous substantially gas is transported in the oxygen expenditure technology.
Oxygen selectivity mixed conductor material is aforesaid perovskite type ceramic.With the oxygen flow of nonnitrogenous substantially gas under being higher than 150 ℃ temperature and be about under the pressure of 1-20 crust and be transported in the oxygen expenditure technology.
In the method, step (a) and (b) is carried out in circulation.Can with air and the product gas flow that lacks oxygen with and the mode input reactor of stream, or this can be with they mode input reactors with adverse current.
It is the gas that is rich in nitrogen that oxygen keeps the accessory substance that produces during the step (a).The step of this method (c) also contains generation the recyclable product gas flow that is used for the carbon dioxide of other purposes.
In another embodiment of the invention, the method for the product gas flow that is formed for oxygen expenditure technology is disclosed, this method may further comprise the steps:
A) with air input by first heat exchanger, and enter in the reactor that contains oxygen selectivity mixed conductor material, on oxygen selectivity mixed conductor material, keep oxygen thus, reactor is being higher than under 300 ℃ the temperature; With
B) second heat exchanger passed through in the air-flow input that will lack oxygen, and by reactor, discharges oxygen from oxygen selectivity mixed conductor material thus, forms product gas flow.
This method is keeping certainly with heat of circulation.Oxygen selectivity mixed conductor material is aforesaid perovskite type ceramic.
The fuel gas adding can be lacked in the air-flow of oxygen, fuel gas is preferably selected from carbon monoxide, hydrogen, methane or its mixture.
The heat exchanger that is used for this method can be a multi channel heat exchanger, arranges first heat exchanger and second heat exchanger, makes them become the combination of inner heat exchanger, external heat exchanger and inner heat exchanger and external heat exchanger.
Can and lack in the mode input reactor of air-flow with adverse current of oxygen air.In this method that forms air-flow, during keeping step (a), oxygen produced the gas that is rich in nitrogen as accessory substance.
The temperature that second heat exchanger will lack the air-flow of oxygen is brought up to about 900 ℃, can contain about at the most 5% oxygen in this air-flow.
Describing in the process of the present invention by the mode of schematic diagram with by embodiment, with the equipment of boiler as representative oxygen expenditure technology.Be to be understood that the inventive method to be applied to other oxygen expenditure technology, as oxidizing hydrocarbons, the selective oxidation processes that is used to produce chemicals, burning, gasification etc. wholly or in part.
Brief Description Of Drawings
Fig. 1 is the figure that implements boiler of the present invention and ceramic oxygen generation system.
Fig. 2 implements the figure that the ceramic oxygen that is used for the oxygen-fuel application of the present invention produces system.
Fig. 3 implements the figure that the ceramic oxygen with steam flusher of the present invention produces system.
Fig. 4 shows that the ceramic oxygen of layered arrangement produces the figure of reactor.
The detailed description of preferred implementation
Fig. 1 is the exemplary embodiment of oxygen expenditure process equipment such as boiler or fired heater and oxygen generation ceramic system B.What adorned among the B is oxygen selectivity ceramic material.Pipeline 10 feeds boiler A with fuel gas.Fuel can be selected from CH
4, H
2, CO, C
2H
4, C
2H
6And composition thereof, maybe can be coal, charcoal or other solid and various refinery flares stream, fuel oil etc., or any suitable combustible material.The burning discharge gas or the flue gas that mainly comprise carbon dioxide and steam are left burning/heating recovery zone A by pipeline 12.Gas is discharged in part burning produce the B of system by pipeline 14 aerating oxygens.Compressed air enters oxygen by pipeline 20 and produces system.The oxygen poor air communication piping 22 that mainly contains up to 98% nitrogen leaves oxygen generation system.Oxygen from air is retained on the oxygen selectivity ceramic material.Burning is discharged gas and is entered the B of system, and the oxygen of removing wherein makes ceramic material regeneration.This gas leaves and enters boiler A by the gas that is rich in oxygen of the nonnitrogenous substantially gas of pipeline 18 conducts, can burn again thus.
Ceramic system mainly comprises at least 2 reactors of filling high-temperature oxygen selectivity ceramic material such as perovskite material, and is used for the inert ceramic material of internal heat exchange, optional multi channel heat exchanger and switching valve.This method circulates, and is similar with the pressure oscillation reservation method.Say that briefly air is fed first bed, and oxygen preferably is retained on wherein the material, the air-flow of oxygen poor is discharged from this top then.In case material to small part by oxygen saturated after, just with transition of operation in another container.Now, discharge the flue gas of gas or circulation with burning and wash first bed, they can remove oxygen at least in part, make material regeneration.At least need two reactors, to guarantee continued operation.
Try Fig. 2 now,, behind multi channel heat exchanger, will in the bed high-temperature oxygen selectivity ceramic material such as perovskite material be housed by in these with the air compression.Oxygen is retained on the perovskite, and nitrogen leaves this bed as effluent.Then, this effluent air-flow will leave the circulatory system then once more by one in the multi channel heat exchanger.When bed is carrying out step that air passes through, wash second saturated perovskite bed of part oxygen with the flue gas of circulation.Just as air, the flue gas of circulation is also by multi channel heat exchanger, then by the perovskite bed.When the flue gas of circulation was passed through this, the oxygen desorption that it will be stored on the perovskite came out, and also made perovskite regeneration.Then, the gas that is rich in oxygen leaves this bed by the multichannel interchanger, with the flue gas generation heat exchange of the circulation that enters.
The flue gas of having described bed B in the step that air passes through and circulation among Fig. 2 is by being the bed A in the regeneration step.At first air is compressed to required pressure with air blast E.Then compressed air is imported among the multi channel heat exchanger G by valve V5.Valve V6 closes in this step.Carry out heat exchange by the air-flow 16 with the oxygen poor of returning, air heats in interchanger G.Among the air 14 input perovskite bed B with heating.The air-flow 15 of oxygen poor leaves a B, with the air that enters heat-shift in heat exchanger G, leaves this system by valve 8 as air-flow 20 then.
At first, cooling is compressed in air blast D then from the flue gas from the recirculation of boiler in cooler C, then with it by among the valve V1 input multi channel heat exchanger F.After the heating, allow it pass through the saturated bed A of oxygen.Rich oxygen containing air-flow 35 leaves this bed from the bottom, by interchanger F, enter surge tank H by valve V3.
Provided representational valve sequence in the following table:
| Step | Duration | Bed A | Bed B | Valve | ||||||||
| Second | Feed gas | Feed gas | V1 | V2 | V3 | V4 | V5 | | V7 | V8 | ||
| 1 | 30 | Air | Flue gas | Open | Close | Open | Close | Open | Close | Open | Close | |
| 2 | 30 | Fuel gas | Air | Close | Open | Close | Open | Close | Open | Close | Open | |
The present invention can several modes and oxygen expenditure process equipment such as boiler or fired heater integrate, its objective is and raise the efficiency.In an embodiment of this method, under dysoxidative slightly condition, operate boiler, make flue gas oxygen-free gas but contain a small amount of carbon monoxide and hydrogen.Carbon monoxide and hydrogen burn in the perovskite reactor, produce to keep and improve the required heat of perovskite reactor cycles operation.
Perhaps, operate boiler under certain condition, make full combustion of fuel, have a spot of excessive oxygen in the flue gas, generally be about 0.5 volume %.In this case, in the flue gas input perovskite reactor with circulation, add a small amount of suitable fuel such as carbon monoxide, hydrogen, methane or its combination simultaneously, addition is enough to react with the middle excessive oxygen that exists of flue gas (air-flow 50 among Fig. 2) at least.This burning produces the required heat of cyclic process.Adjust add the amount of fuel gas so that produce enough heats.Adding the oxygen of storing on any excessive fuel and the perovskite reacts.If because burning has produced higher temperature, help from perovskite, to extract more oxygen.
Perhaps, under the condition of excessive oxygen, operate boiler, to guarantee all fuel completing combustions.In this case, flue gas can contain the nearly oxygen of 5% volume.Flue gas has wherein added the above-mentioned fuel gas of controlled quentity controlled variable by an available reactor, and this reactor can be equipped with the catalyst that the catalyst noble metal catalyst is supported.In this reactor by with the reaction consumes oxygen of the fuel gas that adds.As mentioned above, be used for producing oxygen flow in the part input perovskite reactor with the gas that produces after the recuperation of heat then.Combustion catalyst can be individualism or mix in same reactor with perovskite, as the layer at reactor inlet place.Also can be with calcium titanium ore bed as combustion catalyst.
Perhaps, will leave the oxygen-containing gas cooling of perovskite reactor, isolate moisture in the air-flow as condensation water, thereby improve the concentration in the air-flow of oxygen in getting back to oxygen expenditure technology.The oxygen concentration raising helps the oxygen expenditure technological operation, and the operation that can be oxygen expenditure technology provides greater flexibility.A kind of extension of this scheme is only to use steam as regeneration gas, as shown in Figure 3.The major advantage of this scheme is by producing the oxygen of any concentration in the condensation process of cooling off rich oxygen containing air-flow and water vapor condensation being come out.Because this method is operation under low pressure still, so only need the low-pressure water steam.Obtaining of low-pressure water steam is not a problem usually, because the scheme that this paper proposed can be integrated into the part of whole boiler or generator or other oxygen expenditure process equipment.
In one embodiment, before entering in the ceramic oxygen generation system, the flue gas of circulation, make it mainly contain CO from wherein removing moisture
2Have been found that the flushing gas in the oxygen extraction step is CO
2The time, the amount of oxygen that reclaims from ceramic bed is higher than other gas such as N
2Or steam.Think that this is because the CO that heat release keeps in ceramic material
2It is more to cause oxygen to discharge.
The scheme that proposes among Fig. 2 and 3 changes method based on dividing potential drop, and promptly the oxygen partial pressure difference that is kept between step and the extraction step by oxygen provides the driving force of extracting store oxygen.The compressed pressure that reaches of air is mainly by oxygen concentration decision required in the oxygen containing air-flow of richness.According to the present invention, at 15-400psia, preferred 15-100psia, more preferably bubbling air under the pressure of 20-40psia; At 0.1-200psia, preferred 8-50psia more preferably under the 1O-30psia recycles flue gas, makes that the pressure differential between these two air-flows of reactor inlet place maintains between the 5-20psi.
The scheme that this paper proposes relates to the notion that is used for guaranteeing the available heat management.For example, one aspect of the present invention provides the inert material purposes that the reproducibility of catalytic process conducts heat that is used for circulating.Shown the structure of reactor that inert material is housed among Fig. 4.Specifically, this reproducibility is conducted heat and at least one external heat exchanger coupling, to realize heat exchange required in the whole process.By carrying out heat exchange with these inert materials, can obviously reduce the temperature of leaving the reactor thermal current, as be lower than about 900 ℃, preferred low to about 500 ℃.The reduction of this gas flow temperature just can be adopted the low-cost configuration material, cause corresponding cost to reduce, and the operation lifetime of the necessary external heat exchanger of additional heat transfer prolongs.
Though this heat transport schemes can be applied to any cyclic process usually, but it is higher that this heat transport schemes is particularly well-suited in operating temperature, 250 ℃ or higher method according to appointment, wherein be not suitable for the switching valve of high-temperature operation, just require effectively to cool off all thermal currents so that can adopt standard valve.And this heat transport schemes also is well suited for for example heating and cooling time and is shorter than about 1 minute, according to appointment quite short cyclic process circulation timei of 15-60 second.
According to certain embodiments of the present invention, the multichannel compact heat exchanger is used for carry out shifting from the supplemental heat of thermal current.These comprise two external heat exchangers, and they carry out simultaneously operating with the cycling of reactor in circular flow.This heat exchanger also is aided with the inside reproducibility heat exchanger that adopts the inert ceramic material layer.This external heat exchanger allows for example to carry out heat exchange between air and the useless stream of nitrogen gas or between the flue gas of circulation and the rich oxygen containing air-flow between the import of same airflow and outlet.On the other hand, inner reproducibility heat exchange allows for example to carry out heat exchange between air and the rich oxygen containing air-flow and between the flue gas of useless nitrogen and circulation between two different air-flows.This heat exchange principle also can adopt the low temperature switching valve, and improves the reliability of cyclic process.
Has remarkable advantage on the calorifics as the multichannel interchanger of the part of compact heat exchanger classification than conventional shell-and-tube interchanger.They are commercially available, can be used for pressure and the temperature up to 800 ℃ up to 2000 crust.At V.V.Wadekar, CEP is the detailed summary about compact heat exchanger in one piece of article in December, 2000, includes it in this paper as a reference.For high temperature is used, generally make these heat exchangers with stainless steel or other alloy.
Though the multichannel interchanger belongs to the integral part of scheme described herein, also can adjust technological parameter and place the inert material of inside reactor to carry out all heat exchanges so that use.This just can exempt the needs of external heat exchange.On the other hand, also may in heat exchanger, carry out all heat exchanges, thereby exempt the interior needs of reactor vessel inert layer.
A feature of cyclic process is that required product gas flow may be polluted impurity owing to there is vessel space.In this case, this means that the nitrogen that rich oxygen containing air-flow exists in may be by the space when oxygen keeps the step knot pollutes.In order to prevent this situation, can introduce another step.In this step, water steam purge reactor after the oxygen reservation step.This step will be removed the nitrogen that may be present in the space.Now, discharge gas or flue gas flushing reactor with regard to available burning.
Oxygen selectivity ceramic material generally is an oxygen selectivity mixed conductor material, and it at high temperature has very high electronics and oxygen ionic conductivity.These mixed conductor examples of substances are perofskite type oxide, CeO
2Base oxide, Bi
2O
3Base oxide, ZrO
2Base oxide and brownmillerite oxide.In order further to improve its electronics conductance and, some metal can be added to ceramic material, form the ceramic-metal compound to oxygen ionized catalytic activity.This metal can be selected from Cu, Ni, Fe, Pt, Pd, Rh and Ag.
Usually, oxygen selectivity ceramic material by its body mutually in conduct oxygen ions and fill the oxygen room and keep oxygen.The oxygen reserve capacity raises with the rising of oxygen partial pressure and the reduction of temperature usually.Therefore, oxygen keep and release steps during, oxygen absorption enters that ceramic material keeps and discharge oxygen from ceramic material can effectively carry out, this is because the oxygen partial pressure of the oxygen partial pressure during the oxygen reservation step when being much higher than the oxygen release steps.
In a preferred implementation, at least a oxygen selectivity ceramic material is optionally mixed ion conductor material and an electronic conductor material of oxygen.In a preferred embodiment, it is A that oxygen selectivity ceramic material comprises structural formula
1-XM
XBO
3-δPerovskite type ceramic, wherein A is metal ion or its mixture of periodic table of elements 3a family and 3b family; M is metal ion or its mixture of periodic table 1a family and 2a family; B is the ion of the d district transition metal of periodic table.X from＞0 to 1; δ is the deviation that replaces the coatings of stoichiometric composition that the A metal ion produces owing to the M metal ion.
In preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and x is about 0.1-1.
In another preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and A is one or more f district lanthanide series.In preferred embodiment, A is La, Y, Sm or its mixture.
In another preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and M is at least a metal of periodic table of elements 2a family.In preferred embodiment, M is Sr, Ca, Ba or its mixture.
In another preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and B is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn or its mixture.In preferred embodiment, B is V, Fe, Ni, Cu or its mixture.
In another preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and x is about 0.2-1.
In another preferred embodiment, at least a oxygen selectivity ceramic material is a perovskite type ceramic, and A is La, Y, Sm or its mixture, and M is Sr, Ca or its mixture, and B is V, Fe, Ni, Cu or its mixture.
In another embodiment, at least a oxygen selectivity ceramic material conductor material is selected from (1) and is selected from Bi
2O
3, ZrO
2, CeO
2, ThO
2, HfO
2And composition thereof ceramic masses, these ceramic masses are doped with CaO; Rare-earth oxide or its mixture; (2) brownmillerite oxide; And (3) their mixture.
In another embodiment, at least a oxygen selectivity ceramic material conductor material is to be selected from Bi
2O
3, ZrO
2, CeO
2, ThO
2, HfO
2And composition thereof at least a ceramic masses, this at least a ceramic masses is doped with and is selected from Y
2O
3, Nb
2O
3, Sm
2O
3, Gd
2O
3And composition thereof rare-earth oxide.
Embodiment
The powder preparation of perofskite type oxide is as follows: at first respective metal oxide or hydroxide are mixed the step of carrying out sintering, ball milling and filtration then, triplicate.Temperature in 3 sintering steps is respectively 900 ℃, 950 ℃ and 1000 ℃, and sintering time is 8 hours.With La
2O
3, Sr (OH)
28H
2O, Ni
2O
3, Co
2O
3And Fe
2O
3Carry out first sintering immediately after doing mixing.Behind each sintering, this material is carried out ball milling with abrasive media and water.Pass through solid collected by filtration behind the ball milling.Allow filter cake 100 ℃ of dried overnight, then that filter cake is broken and grind to form fine powder.Final powder has the Ca-Ti ore type phase structure.
Embodiment 2. makes La
0.2Sr
0.8Co
0.6Fe
0.4O
3-δThe perovskite extrudate.
Adding in the perofskite type oxide powder of about 5 weight % hydroxyethylcelluloses and 14.5 weight % water preparation in the embodiment 1 makes it be transformed into the powder slurry.Allow thus obtained powder starch age overnight, then it is joined in the extruder, be squeezed into extrudate (3 millimeters of diameters, 4 millimeters of length).With dry 2 hours of this extrudate, 600 ℃ of calcinings were 5 hours then in 90 ℃ baking oven.At last, this extrudate of 1050 ℃ of sintering 8 hours.Final extrudate porous and mechanical strength height.
Embodiment 3.
The extrudate of preparation among the embodiment 2 is packed in the tubular reactor of being made by high-temperature metal alloys.The structure of this reactor can make input air, CO to reactor from reactor top or bottom as required
2Air-flow with steam.Control air flow rate with mass flow controller.With PLC control temperature of reactor and valve.Product gas flow and waste gas stream during flushing and the oxygen reservation step are collected in the jar, analyze their average composition with gas analyser and GC.In experiment, temperature of reactor is controlled at 825 ℃.Per 30 seconds with the air stream of 7.6slpm or the CO of 4.7slpm
2Air-flow is with in the reflux type input reactor.At bubbling air and feeding CO
2During the step, respectively reactor pressure is controlled at 23.7psia and 18.7psia.During last 2 seconds of step that bubbling air passes through, reactor pressure is reduced to 18.7psia from 23.7psia.Feed CO
2Average product during the step consists of: 27.8%O
2, 67.1%CO
2And 7.4%N
2, and the waste gas stream that produces during the step that bubbling air passes through contains 2.3%O
2, 12.5%CO
2And 83.5%N
2This proves that available method production disclosed by the invention mainly contains CO
2And O
2Rich oxygen containing air-flow.
Embodiment 4.
In this experiment, per 30 seconds CO with the air of 7.6slpm stream and 4.5slpm
2+ steam mixture air-flow is alternately imported as in the embodiment 3 described reactors with reflux type.At bubbling air and feeding CO
2During+steam the step, respectively reactor pressure is controlled at 23.7psia and 18.7psia.Feed CO
2Average product during the+steam step is formed (in dry base): 40.8%O
2, 44.5%CO
2And 14.7%N
2, and the waste gas stream that produces during the step that bubbling air passes through contains 3.7%O
2, 11.4%CO
2And 84.9%N
2This presentation of results can be used CO
2Produce rich oxygen containing air-flow as flushing gas with the method for the invention with mixture of steam.
Embodiment 5.
In this experiment, the per 30 seconds steam with the air of 7.6slpm stream and 6.2slpm flows and alternately imports in the embodiment 3 described reactors with reflux type.During bubbling air and steam step, respectively reactor pressure is controlled at 23.7psia and 18.7psia.Average product during the feeding steam step is formed (in dry base) and is: 70.4%O
2And 29.6%N
2, and the waste gas stream that produces during the step that bubbling air passes through contains 0.3%O
2And 99.7%N
2(other the non-oxygen gas that contains trace).This result shows that the available water steam produces rich oxygen containing air-flow as flushing gas with the method for the invention.
Table 1 embodiment 3-5 brief summary as a result
| Embodiment # | Product | Waste gas stream | ||||||||
| Flow | O 2％ | CO 2％ | H 2O％ | N 2％ | Flow | O 2％ | CO 2％ | N 2％ | ||
| 3 | Do wet | 5.36 5.36 | 27.8 27.8 | 67.1 67.1 | 0 0 | 7.4 7.4 | 7.02 7.02 | 2.3 2.3 | 12.5 12.5 | 83.4 83.4 |
| 4 | Do wet | 3.82 6.06 | 40.8 25.7 | 44.5 28.1 | 0 37.0 | 14.7 9.3 | 5.75 5.75 | 3.7 3.7 | 11.4 11.4 | 84.9 84.9 |
| 5 | Do wet | 3.37 9.59 | 70.3 24.9 | 0 0 | 0 64.9 | 29.6 10.4 | 6.99 6.99 | 0.3 0.3 | 0 0 | 99.7 99.7 |
Table 1 brief summary the result of embodiment 3-5, and compared in wet, comprise in the product gas flow that promptly the product of steam is formed.As implied above, in the product in the O of moist base
2Concentration is with CO
2The increase of concentration in flushing gas and increasing, this illustrates CO
2Power of regeneration stronger than steam.As described in these embodiment, because still there are some nitrogen in the space in the reactor in product gas flow.Can easily from the space, remove these nitrogen by an additional step between air and flushing gas step.
Though described the present invention according to specific embodiment more of the present invention, it will be understood by those skilled in the art that many other forms of the present invention and modification are conspicuous.Claims of the present invention should be interpreted as having covered all these conspicuous form and the modifications in true spirit of the present invention and scope usually.
Claims (10)
1. method that is formed for the product gas flow of oxygen expenditure technology, this method may further comprise the steps circularly:
A) input air keeps oxygen thus by the reactor of oxygen selectivity mixed conductor material is housed on oxygen selectivity mixed conductor material, and the temperature of described reactor is higher than 300 ℃; With
B) import the air communication that lacks oxygen and cross described reactor, discharge oxygen from described oxygen selectivity mixed conductor material thus.
2. the method for claim 1 is characterized in that, generation was rich in the gas of nitrogen as accessory substance during oxygen kept step (a).
3. the method for claim 1 is characterized in that, has more than one reactor.
4. the method for claim 1 is characterized in that, with described air and the described air-flow that lacks oxygen with and the mode of stream or adverse current import in the described reactor.
5. the method for claim 1 is characterized in that, described oxygen selectivity mixed conductor material is that structural formula is A
1-XM
XBO
3-δPerovskite type ceramic.
6. method as claimed in claim 5 is characterized in that A is a rare earth element ion, and M is Sr, Ca, Ba, V or its mixture; B is Co, Mn, Cr, Fe or its mixture; X is from greater than 0 to about 1; δ replaces rare earth element ion and the deviation for coatings of stoichiometric composition that produces by Sr, Ca and Ba.
7. method as claimed in claim 6 is characterized in that x is about 0.1-1.
8. the method for claim 1 is characterized in that, produces the oxygen flow of nonnitrogenous substantially gas during step (b).
9. method as claimed in claim 8 is characterized in that, in the oxygen flow input oxygen expenditure technology with described nonnitrogenous substantially gas.
10. the method for claim 1 is characterized in that, described oxygen expenditure technology is selected from chemical oxidation process, partial oxidation technology, boiler technology, burning process and gasifying process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/092,345 | 2005-03-29 | ||
| US11/092,345 US7303606B2 (en) | 2002-01-08 | 2005-03-29 | Oxy-fuel combustion process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1840965A true CN1840965A (en) | 2006-10-04 |
Family
ID=37030095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100741199A Pending CN1840965A (en) | 2005-03-29 | 2006-03-28 | Oxy-fuel combustion process |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20060105465A (en) |
| CN (1) | CN1840965A (en) |
| AU (1) | AU2006200824A1 (en) |
| SG (1) | SG126042A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100288B (en) * | 2007-06-08 | 2010-09-29 | 清华大学 | System and method for preparing O2-CO2 mixed gas from air |
| CN110678246A (en) * | 2017-04-28 | 2020-01-10 | 亚历山大·塔施 | Material for storing and releasing oxygen |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013202713A1 (en) | 2013-02-20 | 2014-08-21 | Technische Universität Dresden | Producing synthesis gas, involves gasifying carbonaceous gasification material with oxygen-containing gasification agent, and introducing hot synthesis gas and water-containing coolant into evaporator and high-temperature heat exchanger |
-
2006
- 2006-02-27 AU AU2006200824A patent/AU2006200824A1/en not_active Abandoned
- 2006-03-03 SG SG200601312A patent/SG126042A1/en unknown
- 2006-03-27 KR KR1020060027445A patent/KR20060105465A/en not_active Application Discontinuation
- 2006-03-28 CN CNA2006100741199A patent/CN1840965A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100288B (en) * | 2007-06-08 | 2010-09-29 | 清华大学 | System and method for preparing O2-CO2 mixed gas from air |
| CN110678246A (en) * | 2017-04-28 | 2020-01-10 | 亚历山大·塔施 | Material for storing and releasing oxygen |
Also Published As
| Publication number | Publication date |
|---|---|
| SG126042A1 (en) | 2006-10-30 |
| AU2006200824A1 (en) | 2006-10-19 |
| KR20060105465A (en) | 2006-10-11 |
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