CN1298411C - Fuel combustion method with oxygen - Google Patents
Fuel combustion method with oxygen Download PDFInfo
- Publication number
- CN1298411C CN1298411C CNB031009832A CN03100983A CN1298411C CN 1298411 C CN1298411 C CN 1298411C CN B031009832 A CNB031009832 A CN B031009832A CN 03100983 A CN03100983 A CN 03100983A CN 1298411 C CN1298411 C CN 1298411C
- Authority
- CN
- China
- Prior art keywords
- oxygen
- gas
- air
- combustion
- rich
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y02E20/344—
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 require to be filed on January 8th, 2002 interim U.S. Patent application 60/346,582, be filed on January 8th, 2002 60/346,597 and be filed in 60/347,268 the priority on January 10th, 2002.
Technical field
The present invention relates to produce the air-flow that is rich in oxygen, be specifically related to the combustion method of fuel and oxygen.
Background technology
The main purpose of combustion process is to produce heat.In power plant or industrial boiler system, heat is utilized to produce HCS, this HCS can then be used to provide industrial heat or can be used for the generating.Most conventional combustion processes uses air to originate as oxygen.But the existence of nitrogen is inoperative to combustion process in the air, even can have problems on the contrary.For example, nitrogen meeting and oxygen reaction form nitrogen oxide (NO under ignition temperature
x), this is a kind of inappropriate pollutant.In many cases, the product of burning must make it to be lower than environmentally acceptable limit through handling to reduce the discharging of nitrogen oxide.And the existence of nitrogen has improved the volume of burning gases, has increased heat loss thus, so reduced the thermal efficiency of combustion process.In addition, because the high nitrogen content in the burning gases, people are with regard to the not very willing CO that incites somebody to action wherein
2Reclaim or its absorption is removed as product.The CO that emphasizes at present
2Therefore absorption can alleviate its adverse effect to global warming, studies a kind ofly can remove CO with the cost effective and efficient manner
2Process be very important.
A kind of mode of exempting nitrogen from burnt gas or flue gas is to use pure oxygen to replace air in combustion process.But, can produce very high temperature with oxygen combustion, so the flue gas of some generation must be recycled the arrival moderate temperature.Thus oxygen content is diluted to about 27% (all the other～73% be CO
2And keep flame temperature and water), to identical value.Though this scheme can be eliminated the problem relevant with nitrogen, the oxygen cost is too high at present, so that lacks attraction at economic aspect.
In U.S. Patent No. 5,888, discussed in 272 and used ion migration ceramic membrane to carry out the production of oxygen-enriched stream, disclosed the method that feed stream is separated into the air-flow of the rich oxygen containing air-flow that is used for burner and oxygen deprivation.Be about to the feed stream compression, use then to comprise that the ion transferring module with the ion transport membrane that can be detained face and permeable to isolate oxygen from the compression feed stream.Permeable of described ion transport membrane dashes and blows with burn in burner at least a portion of combustion product air-flow of acquisition of the air-flow that is flowed out by ion transferring module permeable face.The shortcoming that this method is produced oxygen is the manufacturing cost height of described film, and it is very difficult to make the leakage-preventing membrane structure of energy.And the rate of recovery of oxygen is lower usually in film unit.
The present invention prepares the unazotized substantially oxygen flow that is applicable to fuel and oxygen burning purposes based on the high temperature oxygen selectivity ceramic material that particle form is made in use, and a kind of attractive alternative of energy that reduces the oxygen cost can be provided.This system's working pressure revolution or temperature switchback mode are very big because the oxygen of ceramic membrane delay load is influenced by temperature and pressure.Described method has several advantages generally at the temperature operation that is higher than 300 ℃, comprises the load height of oxygen, and the selectivity of oxygen is also high.The major advantage of this method is used conventional granular oxygen selective material in the fixed bed reactors that are to use conventional method to design.Therefore, compare the special manufacturing of above-mentioned needs, sealing and assembling process and the known film based method that has some problems in these areas, the method for the invention is easier to commercial Application.Another advantage of described fixed bed ceramic base system is that it can directly prepare and contains the air-flow that oxygen is substantially free of nitrogen, and wherein the concentration of oxygen is suitable for the purposes of fuel and oxygen burning.This point is different from conventional method, and as the air cooling separation method, this method is at first produced high purity oxygen gas, and dilution subsequently obtains required oxygen concentration.
The present invention is applicable to that by production the unazotized substantially oxygen flow of combustion process reduces the cost of oxygen.It relates to uses high-temperature oxygen generation system to produce unazotized substantially oxygen flow.In specific words, the present invention illustrates and uses the oxygen selective ceramic material to come that separated oxygen prepares oxygen flow from air stream that described oxygen flow can be used as the source of oxygen that replaces air and is used for the process that Industrial Boiler or burning heater or other are base with the burning.
Summary of the invention
The invention provides a kind of preparation method who is used for the oxygen flow of Industrial Boiler or burning heater.This method is described as follows: use a part from boiler, mainly contain water vapour and CO
2The flue gas reactor that dash to purge the high temperature oxygen selectivity ceramic material (for example perovskite) that contains oxygen saturated prepare oxygen flow.Described oxygen flow and fuel are imported in the boiler furnace together, and burning therein produces heat.Mode with circulation is exposed to described oxygen deprivation ceramic material in the air, makes it saturated with oxygen.Therefore, the method for operating of described ceramic system is made up of two steps in each circulation of cycling at least.The first step is equipped with the input of air stream in the reactor of high temperature oxygen selectivity ceramic material, and described ceramic material can optionally be detained oxygen.Second step, in the flue gas input reactor of a part, at least a portion oxygen is removed out described ceramic material from boiler furnace, make described material become oxygen deprivation.Described oxygen is detained step and generates heat, and the step of removal oxygen is absorbed heat.On principle, whole pining for property of process, but still there are some heat loss, need be remedied.
In an embodiment of the method, boiler is being operated under the incomplete condition of oxidation a little, thus the flue gas oxygen-free, but contain a spot of CO and H
2Described CO+H
2The oxygen that is kept in ceramic material with a part in reactor burns together, produces to keep the required heat of reactor cycles operation.
In another embodiment of the method, described boiler makes fuel completing combustion, and exists in combustion gas under the condition of a small amount of excessive oxygen (being generally 0.5～5.0 volume %) and operate.In this case, with the flue gas of described circulation and a small amount of suitable fuel gas (CO, H
2, CH
4In, perhaps they mixture) together in the input reactor, add fuel gas amount should be enough at least with flue gas in excessive oxygen reaction.In same reactor, combustion catalyst and oxygen selective ceramic material can be combined, as one deck in import department.And calcium titanium ore bed can play the burning catalyst.This burning has produced the required heat of cyclic process.Regulate the amount of institute's refuelling gas, to produce enough heats.The oxygen reaction that stores in excess of fuel gas that is added and the ceramic material.If because of burning causes higher temperature, then help from ceramic material, to extract more oxygen, this is because the amount of oxygen that is detained in the ceramic material reduces with the rising of temperature usually.Combustion gas also can be passed through another reactor, to adding the fuel gas of controlled quentity controlled variable in this reactor.In the described reactor catalyst can be arranged, as the noble metal catalyst of carrying.Oxygen consumes by being reflected in this reactor with the fuel gas that adds.As mentioned above, after heat recovery, the gas with a part of gained adds in the reactor then, in order to produce oxygen flow.
If use high-temperature valve, from the red-hot flue gas of boiler directly in the input reactor.When using low temperature valve, before entering reactor,, reclaim heat and also produce useful product water steam earlier through over-heat-exchanger from the red-hot flue gas of boiler.The flue gas part of circulation is not after separating moisture and other impurity, can be used to the CO with wherein
2Reclaim.
In another embodiment of the method, will leave the oxygen-containing gas cooling of reactor, condensation separation goes out the moisture in the air-flow, improves the concentration of returning oxygen in the boiler air-flow thus.The concentration of oxygen improves, and just can provide greater flexibility for boiler attendance.
Description of drawings
Fig. 1 is the schematic diagram of boiler of the present invention and ceramic oxygen generation systems.
Fig. 2 is the schematic diagram that the present invention is used for the ceramic oxygen generation systems of fuel and oxygen burning purposes.
Fig. 3 is the present invention dashes the ceramic oxygen generation systems that blows with steam a schematic diagram.
Fig. 4 is the schematic diagram that shows the arrangement of ceramic each layer of oxygen generation systems.
The specific embodiment
Fig. 1 is the schematic diagram of boiler or burning heater A and oxygen generation ceramic system B.The oxygen selective ceramic material is housed in B.Pipeline 10 is transported to fuel gas among the boiler A.Described fuel is selected from CH
4, H
2, CO, C
2H
4, C
2H
6And their mixture, or coal, charcoal or other solid and various refinery flares, fuel oil etc., perhaps any suitable combustible material.The gas that burning is discharged is that flue and combustion gas mainly contain carbon dioxide and water vapour, leaves from burning/heat recovery A by pipeline 12.Part burning is discharged gas and is entered oxygen generation systems B by pipeline 14.Compressed air enters the oxygen generation systems from pipeline 20.The oxygen deprivation air communication piping 22 of mainly nitrogenous (up to 98%) leaves the oxygen generation systems.Oxygen from air just is trapped in the oxygen selective ceramic material.Burning is discharged gas and is entered the B of system, removes oxygen from ceramic material and makes its regeneration.Substantially nonnitrogenous and rich oxygen containing gas leaves by pipeline 18 and enters among the boiler A, burns once more.
Ceramic system mainly comprises at least two inert ceramic materials that are full of high temperature oxygen selectivity ceramic material such as perovskite material and are used for internal heat exchange, multipass heat exchanger and switching valve can also be arranged.The process of system circulates, and can compare with pressure-swing delay process.In brief, air enters first bed, preferentially is trapped on the oxygen selective ceramic material at this oxygen, and the oxygen deprivation air-flow is then extracted out from the top of bed.In case described material is partly by behind the oxygen saturation, operation promptly is transformed into another reaction bed.Dash and blow first bed so discharge gas or cycle flue gas, obtain oxygen, result's this pottery of also just regenerating to small part from this ceramic material with burning.Two reaction beds of minimum needs are to guarantee continued operation.
Try Fig. 2 now, air is compressed, after the multipass heat exchanger, by one in the bed that contains high temperature oxygen selectivity ceramic material such as perovskite material.Oxygen just is trapped on the described perovskite, and nitrogen leaves described bed as discharging gas.This discharges air-flow and passes through in the multipass heat exchanger one once more then, leaves the circulatory system.When a bed carries out the air-treatment step, with the flue gas stream of circulation dash blow another fractional saturation the bed of oxygen.As air, described cycle flue gas also passed through the multipass heat exchanger before by described another perovskite bed.When the described bed of described cycle flue gas process, it has taken away the oxygen that is stored in the perovskite, and this perovskite of having regenerated.The gas that is rich in oxygen then leaves this bed by the multipass interchanger, gives the described cycle flue gas that enters with exchange heat.
Herein, what Fig. 2 described is that a B is in the air-treatment step, and a bed A to be in the cycle flue gas disposal be regeneration step.At first air is compressed to required pressure with air-blaster E.The air of described compression enters among the multipass heat exchanger G by valve V5.In this step, the V6 valve cuts out.The oxygen deprivation air-flow 16 that air returns in interchanger G neutralization carries out heat exchange and is heated.The air 14 of described heating feeds among the perovskite bed B.Oxygen deprivation air-flow 15 leaves a B, and the air exchange heat in that interchanger G neutralization enters leaves system as air-flow 20 through valve V8 then.
The cycle flue gas that leaves boiler cools off in cooling device C, is compressed in air blast D before it is entered multipass heat exchanger F by valve V1 then.After the heating, cycle flue gas process is by oxygen-saturated bed A.The air-flow 35 that has been rich in oxygen leaves bed from the bottom of bed, through interchanger F, enters surge tank H through valve V3 again.
In following table, provide the order that typical valve is opened and closed:
| Step | Duration | Bed A | Bed B | Valve | |||||||
| Second | Charging | Charging | V1 | V2 | V3 | V4 | V5 | V6 | V7 | V8 | |
| 1 | 30 | Air | Flue gas | Open | Close | Open | Close | Open | Close | Open | Close |
| 2 | 30 | Flue gas | Air | Close | Open | Close | Open | Close | Open | Close | Open |
The inventive method can combine with boiler or fired heater in several modes and raise the efficiency.In an embodiment of the method, boiler is to operate under the condition of incomplete oxidation a little, so flue gas oxygen-free gas, but contains a small amount of carbon monoxide and hydrogen.Described carbon monoxide and hydrogen burn in the perovskite reactor, produce to keep and improve the required heat of perovskite cycling.
Boiler also can be in fuel completing combustion, and have a small amount of excessive oxygen in flue gas, is about usually under the condition of 0.5 volume % to operate.In this case, described cycle flue gas and a small amount of suitable fuel gas such as carbon monoxide, hydrogen, methane or their mixture are fed in the perovskite reactor together, the amount that institute adds fuel gas should be enough at least and flue gas (air-flow 50 among Fig. 2) in excessive oxygen react.This combustion process produces the required heat of cyclic process.Regulate the amount of institute's refuelling gas, so that produce enough heats.The oxygen reaction that stores in excess of fuel gas that is added and the perovskite.If because of burning causes higher temperature, then help from perovskite, to extract more oxygen.
Boiler also can also have enough excess of oxygen to guarantee to operate under the condition of all fuel of completing combustion.In this case, the flue gas of generation can contain the oxygen up to 5 volume %.This fuel gas can also be by one toward the reactor that wherein adds above-mentioned controlled quatity fuel gas.Described reactor contains catalyst as holding the noble metal catalyst of lotus.In this reactor, oxygen is by consuming with the fuel gas reaction that is added.As mentioned above, with in a part of gained gas input perovskite reactor after the recuperation of heat, produce oxygen flow then.In this same reactor, combustion catalyst can be what to separate with perovskite, also can be to be combined into the import that one deck is positioned at reactor with perovskite.And calcium titanium ore bed also can play the burning catalyst.
Also can will leave the oxygen-containing gas cooling of perovskite reactor, isolate moisture in the air-flow with the form of condensed water, improve the concentration of returning oxygen in the boiler air-flow thus.This higher oxygen concentration helps the operation of boiler, can provide greater flexibility for boiler attendance.The extension of this scheme is only as regeneration gas, as shown in Figure 3 with steam.Thereby the major advantage of this scheme is the air-flow cooling of will be rich in oxygen condenses water vapour, can produce the oxygen rich gas of any concentration oxygen.Because described method is still under low pressure carried out, and only needs the low-pressure water steam.Because being the part in boiler or power plant as a whole, scheme described here is incorporated into wherein, so obtaining of low-pressure water steam do not become problem usually.
In one embodiment, before cycle flue gas enters ceramic oxygen generation systems, remove moisture wherein, make it mainly by CO
2Form.Have been found that the air blowing body that dashes in the oxygen extraction step is CO
2The time, from the amount of oxygen of ceramic bed recovery, than other gas such as N
2Or water vapour is as higher towards the air blowing body.Think that this is owing to CO on the ceramic material
2Heat generation keep, cause discharging more oxygen.
Scheme shown in Fig. 2 and 3 is based on the dividing potential drop turning course, the driving force of promptly extracting stored oxygen be by oxygen be detained and extraction step between the difference of the oxygen partial pressure that exists provide.The pressure that air compression reaches is mainly by being rich in desired oxygen concentration decision in the Oxygen Flow.According to the present invention, with 15～400psia, be preferably 15～100psia, the pressure input air of better 20～40psia, and cycle flue gas is with 0.1～200psia, be preferably 8～50psia, 10～30psia more preferably makes that the pressure differential at these two air-flows of Reactor inlet maintains between 5～20psi.
Scheme described here relates to uses the notion of guaranteeing that heat effectively utilizes.For example, one aspect of the invention is the use that regenerated heat transmission in the circulation catalytic process provides inert material.In Fig. 4, shown structure of reactor with inert material.Specifically be, use this regenerated heat transmission, shift to obtain the required heat of whole process in conjunction with at least one external heat exchanger.Carried out after the heat exchange with these inert materials, the temperature of leaving the thermal current of reactor can significantly reduce, and for example, is brought down below about 900 ℃, better is low to moderate 500 ℃.This lower gas flow temperature just can be used the low-cost configuration material, makes the corresponding reduction of cost, and degree rises to the service life that additional heat shifts required external heat exchanger.
Though this heat exchange scheme can be used for any cyclic process usually, but it is particularly useful for the higher relatively process of operating temperature, for example, be about 250 ℃ or higher, under the higher situation of this temperature, owing to not can be used for the switching valve of high-temperature operation, have to all thermal current coolings, so that use standard valve.And this heat exchange scheme also is suitable for short cyclic process circulation timei very much, all is shorter than 1 minute, the circulation between for example about 15～60 seconds as those heating and temperature fall time.
According to embodiments of the present invention, use compact multipass heat exchanger to carry out shifting from the supplemental heat of thermal current.Comprise and use two external heat exchangers that they are to operate with the synchronous periodic duty state of reactor cycles operation.Described heat exchange also replenishes by the inside regenerated heat exchange that the inert layer that uses ceramic material carries out.Described external heat exchanger can be in same airflow, for example air, discarded nitrogen or cycle flue gas and be rich in the import of air-flow of oxygen and outlet between carry out heat exchange.On the other hand, inner regenerated heat exchange also can for example be carried out heat exchange between air and rich oxygen containing air-flow and discarded nitrogen and the circulation combustion flue gas at two kinds of different air-flows.The way of this heat exchange also can be used the low temperature switching valve, and improves the reliability of cyclic process.
The multipass interchanger is a kind of of compact heat exchanger class, compares conventional shell-and-tube interchanger and has significant advantage.They can be commercially available, can use up to the pressure of 2000 crust with under up to 800 ℃ temperature.The detailed commentary of compact heat exchanger can be referring to the article of V.V.Wadekar among the CEP in December, 2000, and its content is with reference to being incorporated into this.In order to adapt to high-temperature use, these heat exchangers are made by stainless steel or other alloy usually.
When the multipass interchanger is the whole indispensable parts of scheme described here, also can process parameters, finish all heat exchanges of using the inert material that places inside reactor.So just can eliminate demand to external heat exchanger.On the other hand, also can in heat exchanger, carry out all heat exchanges, and eliminate demand the inside reactor inert layer.
A feature of cyclic process is exactly because the reactor redundant space may cause required product gas flow by contaminating impurity.For this situation, mean that being detained the nitrogen that the air-flow that is rich in oxygen when step finishes exists in can be by redundant space at oxygen pollutes.For fear of this situation, can add a step.In this step, after oxygen is detained step, water steam washing reactor.So just can remove the nitrogen that in the reactor redundant space, exists.Described then reactor just can allow burning discharge gas or flue gas is passed through it.
The oxygen selective ceramic material is the mixed conductor material of oxygen selective normally, and it at high temperature presents the conductivity of high electronics and oxonium ion.The example of these mixed conductors is perofskite type oxide, CeO
2Base oxide, Bi
2O
3Base oxide, ZrO
2Base oxide and brown capillose oxide.In order further to improve the ionization that its electronic conductivity and catalytic activity are used for oxygen, add certain metal phase in the ceramic material in the past, form the ceramic-metal compound.Described metal can be selected from Cu, Ni, Fe, Pt, Pd, Rh and Ag.
Usually, the conduction of described oxygen selective ceramic material by oxonium ion with fill the oxygen vacancies of its integral body in mutually and be detained oxygen.Described oxygen is detained load usually along with increasing with the reduction of temperature of oxygen partial pressure improved.Therefore, in the delay and release steps process of oxygen, can effectively carry out so enter that oxygen in the ceramic material is detained and discharge the back from the oxygen of ceramic material, be because the oxygen partial pressure in being detained step process than the much higher cause of oxygen partial pressure in release steps.
In a preferred implementation, at least a oxygen selective ceramic material is for containing oxygen selective hybrid ionic and electronic conductor.In an embodiment that is more preferably, described oxygen selective ceramic material is that to have structural formula be A
1-xM
xBO
3-δThe perovskite type ceramic material, A is the ion of metal or their mixture in 3a and the 3b family in the periodic table of elements in the formula; M is the ion of metal or their mixture in 1a and the 2a family in the periodic table of elements; B is the ion of d-district transition metal in the periodic table of elements or their mixture; X changes between＞0～1; δ is the deviation for stoichiometric composition that replaces the A metal ion to produce because of the M metal ion.
In an embodiment that is more preferably, this at least a oxygen selective ceramic material is a perovskite type ceramic, and x changes between about 0.1～1.
Be more preferably in the embodiment at another, this at least a oxygen selective ceramic material is a perovskite type ceramic, and A is one or more in the f-district lanthanide series.In the another embodiment that is more preferably, A is La, Y, Sm or their mixture.
In the embodiment that another is more preferably, this at least a oxygen selective ceramic material is a perovskite type ceramic, and M is at least a metal in the 2a family in the periodic table of elements.In the another embodiment that is more preferably, M is Sr, Ca, Ba or their mixture.
In the embodiment that another is more preferably, this at least a oxygen selective ceramic material is a perovskite type ceramic, and B is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn or their mixture.In the another embodiment that is more preferably, B is V, Fe, Ni, Cu or their mixture.
In the embodiment that another is more preferably, this at least a oxygen selective ceramic material is a perovskite type ceramic, and x is about 0.2～1.
Be more preferably in the embodiment at another, this at least a oxygen selective ceramic material is a perovskite type ceramic, and A is La, Y, Sm or their mixture, and M is Sr, Ca or their mixture, and B is V, Fe, Ni, Cu or their mixture.
In another embodiment, this at least a oxygen selective pottery conductor material is:
(1) is selected from Bi
2O
3, ZrO
2, CeO
2, ThO
2, HfO
2With the ceramic masses of their mixtures, described ceramic masses has mixed CaO, rare-earth oxide or their mixture;
(2) brown capillose oxide;
(3) mixture of (1) and (2) described material.
In another embodiment, this at least a oxygen selective ceramic material conductor is for being selected from Bi
2O
3, ZrO
2, CeO
2, ThO
2, HfO
2With at least a ceramic masses in their mixtures, and described at least a ceramic masses mixes and is selected from Y
2O
3, Nb
2O
3, Sm
2O
3, Gd
2O
3With the rare-earth oxide in their mixtures.
Embodiment
Embodiment 1 La
0.2Sr
0.8Co
0.6Fe
0.4O
3-δThe preparation of perovskite powder
At first mix corresponding metal oxide or hydroxide, repeat sintering, ball milling and filtration step three times then, preparation perofskite type oxide powder.Temperature is respectively 900 ℃, 950 ℃ and 1000 ℃ in three sintering steps, and sintering time is 8 hours.Described first sintering is with La
2O
3, Sr (OH)
28H
2O, Ni
2O
3, Co
2O
3And Fe
2O
3Do mixed carrying out immediately afterwards.After each sintering, carry out the ball milling of material with mill Jie and water.Solid collected by filtration after the ball milling.Before filter cake is carried out next sintering, with it 100 ℃ of dried overnight.After the ball milling, tiny powder is pulverized and ground to form to dry cake the last time.The final powder of gained has the Ca-Ti ore type phase structure.
Embodiment 2 La
0.2Sr
0.8Co
0.6Fe
0.40
3-δThe manufacturing of perovskite extrudate
The water that adds about 5 weight % hydroxyethylcelluloses and 14.5 weight % in the perofskite type oxide powder of embodiment 1 preparation is made slurries.With thus obtained slurries age overnight, reinstall extruder and form extrudate (diameter is 3 millimeters, and length is 4 millimeters).With described extrudate in 90 ℃ baking oven dry about 2 hours, then 600 ℃ of roastings 5 hours.Again with extrudate 1050 ℃ of following sintering 8 hours.The extrudate of described final sintering is porous, but mechanical strength is higher.
Embodiment 3
The extrudate that embodiment 2 is made installs in the tubular reactor of being made by high-temperature metal alloys.Described reactor is designed to make air, CO
2Can be on demand feed the reactor with the air-flow of water vapour from the top or the bottom of reactor.The flow of mass flow controller control air-flow.Temperature and valve with PLC control reactor.Blow and be detained in the step process respectively that the product gas flow of gained and off-gas flows are collected in the jar dashing, to analyze its average composition respectively with gas analyzer and gas-chromatography.In this experiment, temperature of reactor is controlled at 825 ℃.With the air stream of 7.6slpm and the CO of 4.7slpm
2Air-flow replaced in the input reactor each 30 seconds with convection type.At air and CO
2In the step process, the pressure of described reactor remains on 23.7psia and 18.7psia separately.When last 2 seconds of air step, the pressure of reactor is reduced to 18.7psia from 23.7psia.At CO
2The product average group becomes in the step: 27.8%O
2, 67.1%CO
2And 7.4%N
2, and the waste gas that produces in the air step contains 2.3%O
2, 12.5%CO
2And 83.5%N
2This has just confirmed mainly to contain CO
2And O
2The air-flow that is rich in oxygen can be with the preparation of disclosed method.
Embodiment 4
In this experiment, with the air stream of 7.6slpm and the CO of 4.5slpm
2+ water vapor mixture stream is alternately imported in the embodiment 3 described reactors each 30 seconds with convection type.At air and CO
2In the process of+steam step, reactor pressure remains on 23.7psia and 18.7psia respectively.At CO
2Average product composition (drying) is in the process of+steam step: 40.8%O
2, 44.5%CO
2And 14.7%N
2, and the waste gas that produces in the air step contains 3.7%O
2, 11.4%CO
2And 84.9%N
2This result shows, with the method that the present invention discloses, uses CO
2Can produce the air-flow that is rich in oxygen with the mixture conduct of water vapour towards the air blowing body.
Embodiment 5
In this experiment, the steam stream of the air of 7.6slpm stream and 6.2slpm is alternately imported in the embodiment 3 described reactors respectively 30 seconds with convection type.In the process of air and water vapour step, reactor pressure remains on 23.7psia and 18.7psia respectively.Average product composition (drying) is in the process of water vapour step: 70.4%O
2, 29.6%N
2, and the waste gas that produces in the air step contains 0.3%O
2And 99.7%N
2(other non-carrier of oxygen that trace is arranged in addition).The result shows, with the method that the present invention discloses, uses water vapour can produce the air-flow that is rich in oxygen as dashing to blow.
Table 1: embodiment 3～5 results' list
| 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 | 3.85 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 24.7 | 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 has been summarized the result among the embodiment 3～5, and compares with the product composition that promptly comprises steam of wet basis.It is as shown in the table, in the wet basis product is formed, and O
2Concentration along with CO in the air blowing body
2The raising of concentration and improving shows CO
2Has stronger power of regeneration than steam.By among the embodiment as seen since reactor in redundant space, in the product water steam, still have some nitrogen.In the air-treatment step with dash to blow and add an additional step between the step and be not difficult from then on to get rid of nitrogen in the redundant space.
Though in conjunction with some concrete embodiments the present invention has been described, for a person skilled in the art, many other embodiments of the present invention and modification are conspicuous.Appending claims of the present invention should be considered as being encompassed in all conspicuous embodiment and modifications in the spirit and scope of the invention usually.
Claims (10)
1. preparation is used in the method for the gas that is rich in oxygen in the combustion zone, and this method comprises the steps:
(a) air is imported gaseous-waste holdup system;
(b) from described air, oxygen is detained on the oxygen selective mixed conductor material;
(c) from described gaseous-waste holdup system, remove nitrogen;
(d) gas that will be rich in oxygen is imported in the described combustion zone;
(e) combustion gas under the described gas existence condition that is rich in oxygen;
(f) will discharge gas from described combustion zone imports in the described gaseous-waste holdup system.
2. the described method of claim 1 is characterized in that CO
2From described discharge gas, reclaim.
3. the described method of claim 1 is characterized in that in the described oxygen gaseous-waste holdup system ceramic adsorbent being housed.
4. the described method of claim 1 is characterized in that described oxygen selective mixed conductor material is to have structural formula A
1-xM
xBO
3-δPerovskite type ceramic, wherein A is a rare earth ion, M is Sr, Ca, Ba, V or their mixture, B is Co, Mn, Cr, Fe or their mixture, x changes between greater than 0 to 1, and δ is because of Sr, Ca and the Ba replacement deviation for stoichiometric composition that rare earth ion produced.
5. the described method of claim 1 is characterized in that described oxygen gaseous-waste holdup system prepares the gas that is rich in oxygen by being detained and blowing the two step processes of dashing.
6. the described method of claim 1 is characterized in that oxygen being adsorbed to fall from the feed stream that contains oxygen.
7. the described method of claim 1 is characterized in that nitrogen is dashed blowing from described gaseous-waste holdup system fall.
8. the described method of claim 1 is characterized in that this method also comprises from described combustion zone recovery heat.
9. the described method of claim 1 is characterized in that described oxygen rich gas is imported boiler combustion with combustion gas.
10. the method for combustion gas in the combustion zone, this method comprises the steps:
(a) described combustion gas is imported in the described combustion zone;
(b) gas that is rich in oxygen that the described method of claim 1 is produced is imported in the described combustion zone;
(c) the described combustion gas of burning;
(d) from described combustion zone, reclaim burning and discharge gas, and be recycled in the described oxygen gaseous-waste holdup system.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34658202P | 2002-01-08 | 2002-01-08 | |
| US34659702P | 2002-01-08 | 2002-01-08 | |
| US60/346,597 | 2002-01-08 | ||
| US60/346,582 | 2002-01-08 | ||
| US34726802P | 2002-01-10 | 2002-01-10 | |
| US60/347,268 | 2002-01-10 | ||
| US10/313,876 | 2002-12-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1432425A CN1432425A (en) | 2003-07-30 |
| CN1298411C true CN1298411C (en) | 2007-02-07 |
Family
ID=27670633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031009832A Expired - Fee Related CN1298411C (en) | 2002-01-08 | 2003-01-08 | Fuel combustion method with oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298411C (en) |
Families Citing this family (3)
| 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 |
| US20170240488A1 (en) * | 2014-12-09 | 2017-08-24 | SABIC Global Technologies B.V | Method for converting methane to ethylene and in situ transfer of exothermic heat |
| CN112161270A (en) * | 2020-07-09 | 2021-01-01 | 河北和和能源科技有限公司 | Heat accumulating type low-nitrogen burner |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888272A (en) * | 1997-06-05 | 1999-03-30 | Praxair Technology, Inc. | Process for enriched combustion using solid electrolyte ionic conductor systems |
| EP0913184A1 (en) * | 1997-10-30 | 1999-05-06 | The Boc Group, Inc. | Elevated temperature adsorption process |
| EP0928938A1 (en) * | 1998-01-06 | 1999-07-14 | Praxair Technology, Inc. | Regenerative oxygen preheat process for oxy-fuel fired furnaces |
| CN1309261A (en) * | 2001-03-29 | 2001-08-22 | 杭州海晨电子有限公司 | Aerating distribution device of burning coal in boiler |
-
2003
- 2003-01-08 CN CNB031009832A patent/CN1298411C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888272A (en) * | 1997-06-05 | 1999-03-30 | Praxair Technology, Inc. | Process for enriched combustion using solid electrolyte ionic conductor systems |
| EP0913184A1 (en) * | 1997-10-30 | 1999-05-06 | The Boc Group, Inc. | Elevated temperature adsorption process |
| EP0928938A1 (en) * | 1998-01-06 | 1999-07-14 | Praxair Technology, Inc. | Regenerative oxygen preheat process for oxy-fuel fired furnaces |
| CN1309261A (en) * | 2001-03-29 | 2001-08-22 | 杭州海晨电子有限公司 | Aerating distribution device of burning coal in boiler |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1432425A (en) | 2003-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1110348C (en) | Process for enriched combustion using solid electrolyte ionic conductor systems | |
| US7303606B2 (en) | Oxy-fuel combustion process | |
| CN1217587A (en) | Solid-electrolyte ionic conductor for producing ratio-adjustable steam-oxygen flow | |
| RU2433341C1 (en) | Method to burn carbon-containing fuel using hard oxygen carrier | |
| CN1269488A (en) | Method for intensifying combustion by solid electrolyte ion conductor system | |
| CN1091633C (en) | Reactive purge for solid electrolyte membrane gas separation | |
| CN1304780A (en) | Method and apparatus for production of carbon dioxide | |
| US20110300060A1 (en) | Oxygen production method and plant using chemical looping in a fluidized bed | |
| AU2003200017B2 (en) | Oxy-fuel combustion process | |
| CN1217586A (en) | Solid-electrolyte ionic conductor system for producing oxygen, nitrogen and/or carbon dioxide | |
| CN113237337B (en) | Cement production carbon capture device and process with waste co-processing | |
| CN1212176A (en) | Hybrid solid electrolyte ionic conductor systems for purifying inert gases | |
| CN1298411C (en) | Fuel combustion method with oxygen | |
| EP2258996B1 (en) | Method for separating blast furnace gas | |
| CN113509834B (en) | Local calcium circulation and pure oxygen combustion coupled cement production carbon capture device and process | |
| CN113200693B (en) | Off-line decomposing furnace and calcium circulation coupled cement production carbon capture device and process | |
| CN109416176B (en) | Combustion system including temperature swing adsorption gas separation | |
| CN1840965A (en) | Oxy-fuel combustion process | |
| JP2019510627A (en) | Multistage adsorption gas separation process and system | |
| CN113120906B (en) | Cement production carbon trapping device and process for treating local calcium circulation coupling waste | |
| CN1196030A (en) | Process and device for separating hydrogen from gas mixture | |
| CN114641451A (en) | Process integrated oxygen supply method for circulating hydrogen engine with inert gas circulation | |
| EP0168073A2 (en) | Method for heat and mass exchange operations | |
| CN114191965B (en) | Automatic many bed layers of continuity decarbonization system of regulation | |
| CN115978532A (en) | Carbon dioxide capture device under pure oxygen burning |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20110108 |