CN110953578B - Chemical chain reaction device with wide load regulation capability and control method thereof - Google Patents
Chemical chain reaction device with wide load regulation capability and control method thereof Download PDFInfo
- Publication number
- CN110953578B CN110953578B CN201911324810.1A CN201911324810A CN110953578B CN 110953578 B CN110953578 B CN 110953578B CN 201911324810 A CN201911324810 A CN 201911324810A CN 110953578 B CN110953578 B CN 110953578B
- Authority
- CN
- China
- Prior art keywords
- reactor
- gas
- air
- fuel
- feed back
- 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.)
- Active
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000033228 biological regulation Effects 0.000 title claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 125
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000001301 oxygen Substances 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 88
- 238000002309 gasification Methods 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000011343 solid material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 description 19
- 239000003245 coal Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 102400000011 Cytochrome b-c1 complex subunit 9 Human genes 0.000 description 3
- 101800000778 Cytochrome b-c1 complex subunit 9 Proteins 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
- F23C10/00—Fluidised bed combustion apparatus
- F23C10/02—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed
- F23C10/04—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone
- F23C10/08—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone characterised by the arrangement of separation apparatus, e.g. cyclones, for separating particles from the flue gases
-
- 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
- F23C10/00—Fluidised bed combustion apparatus
- F23C10/18—Details; Accessories
-
- 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
- F23C10/00—Fluidised bed combustion apparatus
- F23C10/18—Details; Accessories
- F23C10/24—Devices for removal of material from the bed
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a chemical chain reaction device with wide load regulation capability and a control method thereof. The control method is that the oxygen carrier in the oxidation state overflows from the air reactor and enters the fuel reactor through the first material return unit, the oxygen carrier in the reduction state is lifted to a high position in the fuel reactor by utilizing airflow lifting, and then the oxygen carrier returns to the air reactor through the second material return unit to complete a cycle. The invention can realize wide-range load-changing capability, and the load-changing range can reach 30-110%; the material circulation is stable and reliable, and the material circulation quantity can be conveniently regulated and controlled.
Description
Technical Field
The invention relates to the technical field of chemical chains, in particular to a chemical chain reaction device with wide load adjustment capability and a control method thereof.
Background
Chemical looping technology refers primarily to chemical looping combustion (Chemical Looping Combustion) and chemical looping gasification (Chemical Looping Gasification). Chemical looping combustion or gasification is a novel combustion or gasification technology, the key of which is that oxygen in air is transferred to fuel through an oxygen carrier (generally metal oxide), so that direct contact between the fuel and the air is avoided, and the combustion or gasification process can be reducedLosses, combined with a new thermodynamic cycle, can increase the efficiency of the thermodynamic system. Meanwhile, the CO 2 generated by combustion naturally realizes low-cost enrichment in the combustion process. Chemical looping gasification can achieve the effect equivalent to pure oxygen gasification without an air separation oxygen generation system, thereby remarkably reducing gasification cost.
FIG. 1 is a schematic diagram of chemical looping combustion, and the Reactor system mainly comprises an Air Reactor (AR) and a Fuel Reactor (Fuel Reactor, FR). In the air reactor, the reduced oxygen carrier reacts well with air and is oxidized. The oxygen carrier in the oxidized state enters the fuel reactor. The main reactions occurring in the fuel reactor are gasification reactions of fuel (e.g., coal) and reduction reactions of reducing gas to oxygen carrier, respectively. The coal reacts with gasification medium (H 2 O or CO 2) to produce synthesis gas (CO and H 2), which further reacts with the oxygen carrier to produce CO 2 and H 2 O, thereby reducing the oxygen carrier. The reduced oxygen carrier is returned to the air reactor to complete one cycle.
Key technologies for chemical looping combustion include selection of appropriate oxygen carrier materials and rational reaction system and reaction device design. In the technical proposal proposed by the related research of the existing chemical looping combustion, the air reactor mostly adopts a fast fluidized bed, and the fuel reactor has different designs such as a moving bed, a bubbling bed, a fast bed and the like. Different technical schemes relate to circulation of the oxygen carrier solid particle materials between the air reactor and the fuel reactor, and more particularly relate to two movement processes of the oxygen carrier solid particle materials from the air reactor to the fuel reactor and from the fuel reactor to the air reactor.
The movement of the oxygen carrier solid particulate material from the air reactor to the fuel reactor is generally accomplished by carrying the oxygen carrier up through the flow of gas in the air reactor and then into the fuel reactor through a riser and a feed back device driven by gravity. The oxygen carrier solid particle material moves from the fuel reactor to the air reactor in various modes such as movement in a moving bed under the driving of gravity, overflow under the driving of gravity, high carrying by the air flow in the fuel reactor, and entering the air reactor through a vertical pipe and a material returning device under the driving of gravity. Different circulation modes of the oxygen carrier solid particle materials can enable the material circulation to have different stability, reliability, running economy and flexibility of load adjustment.
The existing material circulation mode that the air flow in the air reactor carries the oxygen carrier to the high place and then enters the fuel reactor through the vertical pipe and the material returning device under the driving of gravity makes the circulation quantity depend on the gas flow rate in the air reactor seriously, the gas flow rate depends on the gas flow rate, and the gas flow rate depends on the load rate of the chemical looping combustion device, so when the load rate is determined, the gas flow rate and the gas speed in the air reactor are basically determined, and the gas speed and the load rate are basically in a linear relation. However, the solid circulation amount increases sharply with an increase in gas velocity and decreases sharply with a decrease in gas velocity, which is a serious nonlinear relationship.
This presents a serious problem: if the gas velocity under the design working condition (100% load rate) enables the solid particle amount carried out of the reactor by the gas flow in the air reactor to meet the requirement of chemical looping combustion on the circulation amount, the gas velocity is reduced once the load rate is reduced, the circulation amount is rapidly reduced to the extent that the requirement of chemical looping combustion on the circulation amount cannot be met, namely, the particle circulation mode enables the variable range of the load rate of the device to be small, and the variable load adjustment capability is poor. Or in order to ensure the material circulation quantity under low load, the high air speed (namely, the small cross-sectional area design of the hearth) is required to be maintained under low load, so that the air speed under high load is higher and far exceeds the air speed of a conventional circulating fluidized bed, the abrasion of a heating surface in an air reactor is serious, the problem that the area of a heat absorbing surface (a water cooling wall) in a furnace is insufficient possibly exists, meanwhile, the circulation quantity of the air reactor under high load far exceeds the circulation quantity required by chemical looping combustion, and the excessive circulation quantity requires excessive pressure drop, so that the excessive primary air pressure and the excessive secondary air pressure are required under high load, and the primary air blower and the secondary air blower have excessively high electricity consumption and are uneconomical to operate.
Disclosure of Invention
Aiming at the problems that (1) solid circulation quantity and load rate are coupled in the prior art, the variable load range is narrow, and the operation flexibility is poor; (2) the solid circulation amount is not easy to adjust and control; (3) The invention provides a chemical chain reaction device and a control method thereof, which can realize wide-range variable load capacity, realize stable and reliable material circulation, conveniently adjust and control material circulation quantity, realize reasonable air speed of an air reactor and avoid the problems of high pressure drop, easy wear of a heating surface and the like of the air reactor.
An aspect of the present invention provides a chemical looping reaction apparatus having a wide load adjustment capability, including an air reactor, a fuel reactor, and a first recycle unit disposed between the air reactor and the fuel reactor, and a second recycle unit disposed between the fuel reactor and the air reactor, wherein,
The first feed back unit comprises a first feed back device, a feed inlet of the first feed back device is connected with an overflow hole at the lower side of the air reactor, a discharge hole is connected with a feed back feed inlet at the lower side of the fuel reactor, the feed inlet of the first feed back device is lower than the overflow hole of the air reactor, and the feed back feed inlet of the fuel reactor is lower than the discharge hole of the first feed back device;
The second feed back unit comprises a gas-solid separation unit and a second feed back device, a feed inlet of the gas-solid separation unit is connected with a discharge outlet at the top of the fuel reactor, a solid material discharge outlet of the gas-solid separation unit is connected with a feed inlet of the second feed back device, a discharge outlet of the second feed back device is connected with a feed back inlet at the lower side of the air reactor, the feed inlet of the second feed back device is lower than the discharge outlet of the gas-solid separation unit, and the feed back inlet of the air reactor is lower than the discharge outlet of the second feed back device;
the air reactor is provided with an oxidizing gas inlet and a first gas outlet;
The fuel reactor is provided with a fuel inlet and a second gas outlet.
According to one embodiment of the chemical chain reaction device with the wide load adjustment capability, the air reactor is a circulating fluidized bed and comprises a reactor body, a first separator and a return device, wherein a first gas outlet at the top of the reactor body is connected with a feed inlet of the first separator, a solid material discharge outlet of the first separator is connected with a feed inlet of the return device, a discharge outlet of the return device is connected with a return port at the lower side of the reactor body, the gas velocity of the designed section of the reactor body is 1-10 m/s, and at least two oxidizing gas inlet openings with different heights are arranged on the reactor body.
According to one embodiment of the chemical looping reaction device with wide load adjustment capability, the heating surface is arranged on the inner wall of the reactor body of the air reactor, the air reactor further comprises a fresh oxygen carrier supplementing port connected with the heating surface, the air reactor further comprises an external heat exchange unit arranged between the material returning device and the reactor body, and the external heat exchange unit comprises a particle flow control valve and an external heat exchanger.
According to one embodiment of the chemical looping reaction device with wide load adjustment capability of the invention, the air reactor further comprises a gas purifying and recovering unit connected with the gaseous material outlet of the first separator, and the gas purifying and recovering unit comprises a first heat recovering subunit and a first gas purifying subunit which are sequentially connected according to the material flow direction.
According to one embodiment of the chemical chain reaction device with the wide load adjustment capability, the fuel reactor adopts a two-stage structure, the cross section area of the lower-stage body is larger than that of the upper-stage body, the ratio of the cross section area of the lower-stage body to the cross section area of the upper-stage body is larger than 1 and smaller than or equal to 20, wherein the lower-stage body is a bubbling bed or a turbulent bed, the designed section gas velocity is 0.1-3 m/s, the upper-stage body is a rapid bed or a transport bed, and the designed section gas velocity is 3-20 m/s.
According to one embodiment of the chemical looping reaction device with wide load adjustment capability, the fuel reactor further comprises a gasification medium supply unit connected with a second gas outlet of the gas-solid separation unit, the gasification medium supply unit comprises a second heat recovery subunit, a second gas purification subunit and a recirculation fan which are sequentially connected according to the material flow direction, the recirculation fan is connected with at least two gasification medium inlets with different heights on the fuel reactor, wherein the gasification medium of the fuel reactor is recycled flue gas, and the temperature of the recycled flue gas is controlled to be 100-500 ℃.
According to one embodiment of the chemical looping reaction device with wide load adjustment capability, the fuel reactor further comprises a cooling purification unit connected with the discharge port of the second gas purification subunit and a cooling separation unit connected with the slag hole at the bottom of the fuel reactor, wherein the bottom of the fuel reactor is further provided with a fuel adding port and a fresh oxygen carrier supplementing port.
According to one embodiment of the chemical chain reaction apparatus with wide load regulation capability of the present invention, the first and second return vessels each employ a return vessel in the form of a flow seal valve, the air reactor is capable of operating in a bubbling bed state under a low load, and the gas-solid separation unit employs a cyclone.
The invention also provides a control method of the chemical chain reaction device with wide load adjustment capability, which comprises the steps of feeding primary air and secondary air into an air reactor to react with the oxygen carrier in a reduced state from a fuel reactor, and overflowing the oxygen carrier in an oxidized state in the air reactor into the fuel reactor through a first feed back unit; and sending the gasification medium into a fuel reactor to perform gasification reaction with fuel to generate synthesis gas, reacting the synthesis gas with an oxygen carrier in an oxidation state in the fuel reactor to generate carbon dioxide and water, lifting the reacted oxygen carrier in a reduction state to a high position in the fuel reactor by using airflow lifting, and returning the oxygen carrier to the air reactor through a second feed back unit to complete a cycle.
The control method of the chemical chain reaction device with wide load regulation capability is characterized by controlling the gas speed in the fuel reactor and the lifting and circulating amount of the oxygen carrier in a reduced state by controlling the feeding amount of the gasification medium and the distribution proportion of the gasification medium among gasification medium inlets with different heights in the fuel reactor, wherein the gasification medium is recirculated flue gas from the fuel reactor.
Compared with the prior art, the concrete heat storage and exchange system for peak shaving and heat supply of the thermal power plant has the following advantages:
1) The variable load capacity in a wide range can be realized, and the load variation range can reach 30-110%;
2) The material circulation is stable and reliable, and the material circulation quantity can be conveniently regulated and controlled;
3) The air reactor has reasonable air speed, lower pressure drop of the air reactor, lower power consumption of a fan and difficult abrasion of a heating surface in the air reactor.
Drawings
Fig. 1 shows a schematic diagram of chemical looping combustion.
Fig. 2 shows a schematic diagram of the basic structure of a chemical chain reaction apparatus according to an exemplary embodiment of the present invention.
Fig. 3 shows a detailed structural schematic diagram of a chemical chain reaction apparatus according to an exemplary embodiment of the present invention.
Reference numerals illustrate:
1-air reactor, 2-fuel reactor, 21-lower section body, 22-upper section body, 3-first feed back ware, 4-gas-solid separation unit, 5-second feed back ware, 6-first separator, 7-feed back ware, 8-first heat recovery subunit, 9-first gas purification subunit, 10-second heat recovery subunit, 11-second gas purification subunit, 12-recycle fan, 13-cooling purification unit, 14-cooling separation unit, 15-granule flow control valve, 16-external heat exchanger.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
Fig. 2 shows a schematic diagram of the basic structure of a chemical chain reaction apparatus according to an exemplary embodiment of the present invention.
As shown in fig. 2, the chemical looping reaction apparatus with wide load adjustment capability according to an exemplary embodiment of the present invention includes an air reactor 1, a fuel reactor 2, and a first recycle unit disposed between the air reactor 1 and the fuel reactor 2 and a second recycle unit disposed between the fuel reactor 2 and the air reactor 1.
That is, the movement of the oxygen carrier particulate solid material from the air reactor 1 to the fuel reactor 2 in the present invention does not adopt the conventional manner of returning the material after the air flow is lifted, but rather, the overflow holes are provided at the side surface of the lower part of the air reactor, and the material overflows the air reactor and returns to the fuel reactor through the first return unit. The return material of the fuel reactor 2 to the air reactor 1 lifts the oxygen carrier solid particles to a high position in an airflow lifting mode, and then returns to the air reactor 1 through a second return unit. Wherein the air reactor is provided with an oxidizing gas inlet and a first gas outlet, and the fuel reactor is provided with a fuel inlet and a second gas outlet.
Specifically, the first feed back unit of the invention comprises a first feed back device 3, wherein the feed inlet of the first feed back device 3 is connected with the overflow hole at the lower side of the air reactor 1, the discharge hole is connected with the feed back inlet at the lower side of the fuel reactor 2, the feed inlet of the first feed back device 3 is lower than the overflow hole of the air reactor 1, and the feed back inlet of the fuel reactor 2 is lower than the discharge hole of the first feed back device. By the above structure, the oxygen carrier in the oxidized state after reaction in the air reactor 1 overflows and is fed into the fuel reactor 2 under the action of gravity.
The second feed back unit includes gas-solid separation unit 4 and second feed back ware 5, and the feed inlet of gas-solid separation unit 4 links to each other with the discharge gate at fuel reactor 2 top and the solid material discharge gate of gas-solid separation unit 4 links to each other with the feed back mouth of second feed back ware 5, and the discharge gate of second feed back ware 5 links to each other with the feed back feed inlet of air reactor downside, and the feed inlet of second feed back ware 5 is less than the discharge gate of gas-solid separation unit 4, and the feed back feed inlet of air reactor 1 is less than the discharge gate of second feed back ware 5. Through the structure, the oxygen carrier in the reduced state after reaction in the fuel reactor 2 can be lifted to a high position under the action of air current lifting, and then returned to the air reactor 1 through gas-solid separation.
According to the scheme, the circulation amount of the oxygen carrier in the whole chemical looping combustion depends on the lifting amount of the air flow in the fuel reactor to the oxygen carrier (the flow rate of solid particles can be self-adaptively adjusted because the air reactor returns the oxygen carrier to the fuel reactor by overflow), and the circulation amount of the chemical looping combustion can be controlled by controlling the air speed in the fuel reactor. The gas speed in the fuel reactor can be conveniently controlled by the inlet amount of the gasification medium and is irrelevant to the load rate of combustion, so that the decoupling of the solid circulation amount and the load rate is realized, and the chemical looping combustion device can have wide-range flexible load regulation.
The invention preferably adopts the oxygen carrier with finer particle size of class A or class B particles, which is easy to realize large circulation quantity of the oxygen carrier; the fuel pretreatment system is simple and does not need to prepare powder by adopting the fuel with the coarser particle diameter D particles with the average particle diameter of about 1 mm. The oxygen carrier and the fuel can be oxygen carrier (such as natural ilmenite oxygen carrier) and fuel (such as coal) which are commonly used in chemical chain reaction in the prior art. Wherein class a is fine particles, e.g. on the order of 50 um; class B is a finer particle, e.g., on the order of 150 um; class D is coarse particles, e.g. of the order of 1mm or more.
Wherein, the first material returning device 3 and the second material returning device 5 are both material returning devices in the form of flow sealing valves, the air reactor 1 can operate in a bubbling bed state under low load, and the gas-solid separation unit 4 adopts a cyclone separator.
Fig. 3 shows a detailed structural schematic diagram of a chemical chain reaction apparatus according to an exemplary embodiment of the present invention.
As shown in fig. 3, for further elaboration of the chemical chain reaction apparatus of the present invention, the air reactor 1 of the present invention is a circulating fluidized bed and comprises a reactor body, a first separator 6 and a return 7, wherein a first gas outlet at the top of the reactor body is connected with a feed inlet of the first separator 6, a solid material discharge outlet of the first separator 6 is connected with a feed inlet of the return 7, and a discharge outlet of the return 7 is connected with a return inlet at the lower side of the reactor body. The designed section gas velocity of the reactor body is 1-10 m/s, preferably 3-6 m/s; at least two oxidizing gas inlets with different heights are arranged on the reactor body, and the oxidizing gas (such as air) is divided into at least two flows (primary air and secondary air) which are sent into the air reactor 1 from different heights so as to control the fluidization state and the reaction process in the air reactor.
Further, the heating surface is arranged on the inner wall of the reactor body of the air reactor 1 to remove part of heat released by the reaction and maintain the reaction temperature required by the system, and the air reactor has the advantages of high gas-solid contact efficiency, large unit sectional area treatment capacity, strong heat transfer in the furnace, uniform heat transfer and the like. The air reactor 1 further comprises an external heat exchange unit arranged between the material returning device 7 and the reactor body, wherein the external heat exchange unit comprises a particle flow control valve 15 and an external heat exchanger 16, and when the heat transfer quantity of a heating surface in the furnace is insufficient, the particle flow control valve 15 is opened to enable part of particles to flow through the external heat exchanger 16 so as to remove more heat. The air reactor also includes a fresh oxygen carrier replenishment port connected thereto to properly replenish the fresh oxygen carrier.
In addition, the air reactor 1 further comprises a gas purifying and recovering unit connected with the gaseous material outlet of the first separator 6, the gas purifying and recovering unit comprises a first heat recovering subunit 8 and a first gas purifying subunit 9 which are sequentially connected according to the material flow direction, and high-temperature gas (containing a small amount of O 2 and a large amount of N 2) at the outlet of the air reactor 1 is cooled and recovered by the first heat recovering subunit 8 and is purified by the first gas purifying subunit 9 and then discharged.
The fuel reactor in the invention adopts a two-stage structure, the cross-sectional area of the lower stage body 21 is larger than that of the upper stage body 22, and the ratio of the cross-sectional area of the lower stage body 21 to the cross-sectional area of the upper stage body 22 is larger than 1 and smaller than or equal to 20. The lower section body is a bubbling bed or a turbulent bed, and the designed section gas velocity is 0.1-3 m/s, more preferably 0.5-1.5 m/s; the upper section body is a rapid bed or a transport bed, and the designed section gas velocity is 3-20 m/s, more preferably 5-10 m/s. Wherein the gasifying medium is divided into at least two and fed into the fuel reactor 2 at different elevations of the fuel reactor to control the fluidization state within the fuel reactor 2 such that the lower part of the fuel reactor is a bubbling or turbulent bed and the upper part is a fast or transport bed.
The bubbling bed or turbulent bed at the lower part has higher solid content and lower gas speed, thus having longer time for fuel gasification reaction, so that the fuel gasification reaction with slower chemical reaction can be carried out as fully as possible, and the conversion rate of the fuel is improved. The upper fast or transport bed has a high gas velocity and a sufficiently large solid particle flow rate to be able to provide a sufficient circulation volume. Meanwhile, the upper rapid bed or the transport bed has higher solid content, so that gases such as CO, H 2 and the like generated by the gasification reaction of the fuel at the lower part of the fuel reactor can be oxidized by the oxygen carrier as fully as possible, and the energy loss of unburned gases is reduced.
The gasification medium of the fuel reactor is recycled flue gas, the fuel reactor 2 also comprises a gasification medium supply unit connected with a second gas outlet of the gas-solid separation unit, the gasification medium supply unit comprises a second heat recovery subunit 10, a second gas purification subunit 11 and a recycling fan 12 which are sequentially connected according to the material flow direction, and the recycling fan 12 is connected with at least two gasification medium inlets with different heights on the fuel reactor 2 so as to feed the gasification medium at different heights. By controlling the flow of the recirculated flue gas and the distribution of the flow of the recirculated flue gas between the different injection locations, the amount of material circulation of the oxygen carrier particles between the two reactors can be conveniently regulated and controlled.
The flue gas at the outlet of the fuel reactor 2 passes through the second heat recovery subunit 10 and the second gas cleaning subunit 11 before entering the recirculation fan 12, so as to reduce the working temperature and inlet dust content of the recirculation fan, provide the working reliability of the recirculation fan, and the inlet temperature of the recirculation fan 12 needs to be controlled above the acid dew point of the flue gas and below 500 ℃ to ensure the stable and reliable operation of the dust remover and the fan, and the typical value is between about 100 ℃ and 300 ℃.
Furthermore, the fuel reactor 2 comprises a cooling and purifying unit 13 connected to the outlet of the second gas purifying sub-unit 11 and a cooling and separating unit 14 connected to the slag outlet at the bottom of the fuel reactor 2. Therefore, besides being used for recycling, the flue gas generated by the fuel reactor is subjected to treatments such as further cooling separation, compression purification and the like by the cooling purification unit 13 to obtain liquid water and purer CO 2, so that the capture of CO 2 is realized. For the fuel with large ash content and easy formation of large particle bottom slag, the bottom slag is periodically discharged from the lower part of the fuel reactor 2, so that the accumulation of the large particle bottom slag at the lower part of the fuel reactor is avoided, the stable operation of the device is influenced, and as a part of oxygen carrier is inevitably carried in the discharged bottom slag, the oxygen carrier can be separated out through the cooling separation unit 14 and then recycled.
The first separator 6 in the invention may be a cyclone dust collector, and the first gas purifying subunit 9 and the second gas purifying subunit 11 may be a combination of dust collectors, purifying devices for purifying pollutant gases of S, N and other elements; the first heat recovery subunit 8, the second heat recovery subunit 10 and the cooling and purifying unit 13 can be coolers with water or steam as a medium; the cooling separation unit can be a fluidized bed slag cooler followed by a magnetic separator. But the present invention is not limited thereto.
The invention also provides a control method of the chemical chain reaction device with wide load adjustment capability, which comprises the following steps: the primary air and the secondary air are sent into an air reactor 1 to react with the oxygen carrier in a reduced state from a fuel reactor 2, and the oxygen carrier in an oxidized state in the air reactor overflows and enters the fuel reactor 2 through a first feed back unit; and (3) feeding a gasification medium into the fuel reactor 2 to perform gasification reaction with fuel to generate synthesis gas, reacting the synthesis gas with an oxygen carrier in an oxidation state to generate carbon dioxide and water, lifting the reacted oxygen carrier in a reduction state to a high position in the fuel reactor by using airflow lifting, and returning the oxygen carrier to the air reactor 1 through a second feed back unit to complete one cycle. In the invention, the gas speed in the fuel reactor and the lifting and circulating quantity of the oxygen carrier in a reduced state are controlled by controlling the inlet quantity of the gasification medium in the fuel reactor and the distribution proportion of the gasification medium between gasification medium inlets at different heights, the adopted gasification medium is the recirculated flue gas from the fuel reactor 2, and the rest operation can be specifically adjusted according to the actual working conditions.
The invention will be further illustrated with reference to specific examples.
Examples:
The present example used a natural ilmenite oxygen carrier with an average particle size of about 120 μm and a particle density of 2500kg/m 3 (after activation). The fuel is coal, the coal quality is lignite with high volatile matters and low ash, a fuel crushing and screening treatment system similar to a conventional circulating fluidized bed boiler is adopted, and the average particle size of the coal is 0-10mm and the average particle size of the coal is 1mm.
At 100% load rate:
The average reaction temperature of the air reactor was about 950 ℃, the top pressure was about normal pressure, the cross-sectional gas velocity (under actual temperature pressure conditions) was about 5m/s, and the concentration of the outlet O 2 was about 3%.
The average reaction temperature of the fuel reactor is about 900 ℃, the top pressure is about normal pressure, the lower gas velocity is about 1-2 m/s, and the fuel reactor is in a turbulent bed state; the upper air speed is about 5-10 m/s, and is in a rapid bed or transport bed state;
the high temperature flue gas at the outlet of the fuel reactor 2 is cooled to about 200 c using a second heat recovery sub-unit 10 and a second gas cleaning sub-unit 11 (using a bag-type dust collector).
At 30% load rate:
The average reaction temperature of the air reactor was about 900 ℃, the top pressure was about normal pressure, the gas velocity (under actual temperature pressure conditions) was about 1.5m/s, and the concentration of the outlet O 2 was about 5%.
The average reaction temperature of the fuel reactor is about 850 ℃, the top pressure is about normal pressure, the reduction of the fuel feeding amount leads to the reduction of the gas generation amount in the fuel reactor, but the lower gas speed of the fuel reactor can still be kept between about 1 and 2m/s and is in a turbulent bed state by controlling the recirculation fan 12 to properly increase the gas recirculation amount; the upper gas velocity is still kept between about 5 and 10m/s (adjusted according to the required solid circulation amount) and is in a rapid bed or transport bed state, so that the solid circulation amount of the oxygen carrier is controlled in a required range.
The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (10)
1. A chemical chain reaction device with wide load regulation capability is characterized by comprising an air reactor, a fuel reactor, a first feed back unit arranged between the air reactor and the fuel reactor and a second feed back unit arranged between the fuel reactor and the air reactor, wherein,
The first feed back unit comprises a first feed back device, a feed inlet of the first feed back device is connected with an overflow hole at the lower side of the air reactor, a discharge hole is connected with a feed back feed inlet at the lower side of the fuel reactor, the feed inlet of the first feed back device is lower than the overflow hole of the air reactor, and the feed back feed inlet of the fuel reactor is lower than the discharge hole of the first feed back device;
The second feed back unit comprises a gas-solid separation unit and a second feed back device, a feed inlet of the gas-solid separation unit is connected with a discharge outlet at the top of the fuel reactor, a solid material discharge outlet of the gas-solid separation unit is connected with a feed inlet of the second feed back device, a discharge outlet of the second feed back device is connected with a feed back inlet at the lower side of the air reactor, the feed inlet of the second feed back device is lower than the discharge outlet of the gas-solid separation unit, and the feed back inlet of the air reactor is lower than the discharge outlet of the second feed back device;
the air reactor is provided with an oxidizing gas inlet and a first gas outlet;
The fuel reactor is provided with a fuel inlet and a second gas outlet.
2. The chemical looping reaction device with wide load adjustment capability according to claim 1, wherein the air reactor is a circulating fluidized bed and comprises a reactor body, a first separator and a return device, wherein a first gas outlet at the top of the reactor body is connected with a feed inlet of the first separator, a solid material discharge outlet of the first separator is connected with a feed inlet of the return device, a discharge outlet of the return device is connected with a return port at the lower side of the reactor body, the gas velocity of the reactor body in a design section is 1-10 m/s, and at least two oxidizing gas inlet ports with different heights are arranged on the reactor body.
3. The chemical looping reaction apparatus with wide load capacity according to claim 2, wherein a heating surface is disposed on an inner wall of a reactor body of the air reactor, the air reactor further comprises a fresh oxygen carrier replenishment port connected thereto, the air reactor further comprises an external heat exchange unit disposed between the material returning device and the reactor body, the external heat exchange unit comprising a particle flow control valve and an external heat exchanger.
4. The chemical looping reaction apparatus with wide load capacity according to claim 2, wherein said air reactor further comprises a first gas treatment unit connected to a gaseous material outlet of a first separator, said first gas treatment unit comprising a first heat recovery subunit and a first gas purification subunit connected in sequence according to a material flow direction.
5. The chemical looping reaction apparatus with wide load capacity according to claim 1, wherein the fuel reactor adopts a two-stage structure and the cross-sectional area of the lower-stage body is larger than the cross-sectional area of the upper-stage body, the ratio of the cross-sectional area of the lower-stage body to the cross-sectional area of the upper-stage body is larger than 1 and smaller than or equal to 20, wherein the lower-stage body is a bubbling bed or a turbulent bed and the designed cross-sectional air velocity is 0.1-3 m/s, and the upper-stage body is a rapid bed or a transport bed and the designed cross-sectional air velocity is 3-20 m/s.
6. The chemical looping reaction apparatus with wide load capacity according to claim 5, wherein said fuel reactor further comprises a second gas treatment unit connected to a second gas outlet of the gas-solid separation unit, said second gas treatment unit comprising a second heat recovery subunit, a second gas purification subunit and a recirculation fan connected in sequence according to the flow direction of the material, said recirculation fan being connected to at least two gasification medium inlets of different heights on the fuel reactor, wherein the gasification medium of the fuel reactor is a recirculated flue gas, and the temperature of said recirculated flue gas is controlled between 100 ℃ and 500 ℃.
7. The chemical looping reaction apparatus with wide load capacity according to claim 6, wherein said fuel reactor further comprises a cooling purification unit connected to a discharge port of the second gas purification subunit and a cooling separation unit connected to a slag hole at the bottom of the fuel reactor.
8. The chemical looping reaction apparatus with wide load capacity according to claim 1, wherein said first and second return means are both return means in the form of flow sealing valves, said air reactor is capable of operating in bubbling bed mode at low load, and said gas-solid separation unit is a cyclone.
9. The control method of a chemical looping reaction apparatus having wide load adjustment capability according to any one of claims 1 to 8, characterized in that primary air and secondary air are fed into an air reactor to react with oxygen carrier in a reduced state from a fuel reactor, and oxygen carrier in an oxidized state in the air reactor overflows into the fuel reactor through a first feed back unit; and sending the gasification medium into a fuel reactor to perform gasification reaction with fuel to generate synthesis gas, reacting the synthesis gas with an oxygen carrier in an oxidation state in the fuel reactor to generate carbon dioxide and water, lifting the reacted oxygen carrier in a reduction state to a high position in the fuel reactor by using airflow lifting, and returning the oxygen carrier to the air reactor through a second feed back unit to complete a cycle.
10. The method for controlling a chemical looping reaction apparatus having wide load capacity according to claim 9, wherein the gas velocity and the lift and circulation amount of the reduced oxygen carrier in the fuel reactor are controlled by controlling the amount of the gasification medium introduced into the fuel reactor and the distribution ratio of the gasification medium between the gasification medium inlets at different heights, wherein the gasification medium is the recirculated flue gas from the fuel reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911324810.1A CN110953578B (en) | 2019-12-20 | 2019-12-20 | Chemical chain reaction device with wide load regulation capability and control method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911324810.1A CN110953578B (en) | 2019-12-20 | 2019-12-20 | Chemical chain reaction device with wide load regulation capability and control method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110953578A CN110953578A (en) | 2020-04-03 |
| CN110953578B true CN110953578B (en) | 2024-06-11 |
Family
ID=69983129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911324810.1A Active CN110953578B (en) | 2019-12-20 | 2019-12-20 | Chemical chain reaction device with wide load regulation capability and control method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110953578B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087028A (en) * | 1992-06-08 | 1994-05-25 | 福斯特·惠勒能源公司 | Fluidized bed reactor system and method with a heat exchanger |
| EP0745206A1 (en) * | 1994-02-18 | 1996-12-04 | THE BABCOCK & WILCOX COMPANY | Method and apparatus for controlling the bed temperature in a circulating fluidized bed reactor |
| US5601039A (en) * | 1992-05-21 | 1997-02-11 | Foster Wheeler Energia Oy | Method and apparatus for providing a gas seal in a return duct and/or controlling the circulating mass flow in a circulating fluidized bed reactor |
| JPH1114029A (en) * | 1997-06-19 | 1999-01-22 | Takuma Co Ltd | Circulating fluidized bed combustion equipment and method of operation |
| CA2760959A1 (en) * | 2009-05-19 | 2010-11-25 | Alstom Technology Ltd | Oxygen fired steam generator |
| CN202546742U (en) * | 2012-03-23 | 2012-11-21 | 华北电力大学 | Two-stage double-bed reactor-based solid fuel chemical-looping combustion system |
| CN202927835U (en) * | 2012-11-22 | 2013-05-08 | 青岛畅隆电力设备有限公司 | Tube bundle type cylindrical slag cooler |
| CN103423737A (en) * | 2012-05-25 | 2013-12-04 | 中国科学院工程热物理研究所 | Circulating fluidized bed system having pneumatic control distributing valve, and circulating fluidized bed loop system |
| JP2014234935A (en) * | 2013-05-31 | 2014-12-15 | 株式会社タクマ | Circulating fluidized bed boiler |
| JP2015081203A (en) * | 2013-10-21 | 2015-04-27 | 三菱日立パワーシステムズ株式会社 | Chemical looping combustion system |
| CN104848207A (en) * | 2015-04-07 | 2015-08-19 | 东南大学 | Chemical looping combustion device for solid fuel grading oxidation and method thereof |
| CN106247323A (en) * | 2016-09-14 | 2016-12-21 | 东南大学 | A kind of chemical chain combustion apparatus based on tower bubbling fluidized bed fuel reactor and method thereof |
| CN211667810U (en) * | 2019-12-20 | 2020-10-13 | 东方电气集团东方锅炉股份有限公司 | Chemical chain reaction device with wide load regulation capacity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9765961B2 (en) * | 2015-03-17 | 2017-09-19 | Saudi Arabian Oil Company | Chemical looping combustion process with multiple fuel reaction zones and gravity feed of oxidized particles |
-
2019
- 2019-12-20 CN CN201911324810.1A patent/CN110953578B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5601039A (en) * | 1992-05-21 | 1997-02-11 | Foster Wheeler Energia Oy | Method and apparatus for providing a gas seal in a return duct and/or controlling the circulating mass flow in a circulating fluidized bed reactor |
| CN1087028A (en) * | 1992-06-08 | 1994-05-25 | 福斯特·惠勒能源公司 | Fluidized bed reactor system and method with a heat exchanger |
| EP0745206A1 (en) * | 1994-02-18 | 1996-12-04 | THE BABCOCK & WILCOX COMPANY | Method and apparatus for controlling the bed temperature in a circulating fluidized bed reactor |
| JPH1114029A (en) * | 1997-06-19 | 1999-01-22 | Takuma Co Ltd | Circulating fluidized bed combustion equipment and method of operation |
| CA2760959A1 (en) * | 2009-05-19 | 2010-11-25 | Alstom Technology Ltd | Oxygen fired steam generator |
| CN202546742U (en) * | 2012-03-23 | 2012-11-21 | 华北电力大学 | Two-stage double-bed reactor-based solid fuel chemical-looping combustion system |
| CN103423737A (en) * | 2012-05-25 | 2013-12-04 | 中国科学院工程热物理研究所 | Circulating fluidized bed system having pneumatic control distributing valve, and circulating fluidized bed loop system |
| CN202927835U (en) * | 2012-11-22 | 2013-05-08 | 青岛畅隆电力设备有限公司 | Tube bundle type cylindrical slag cooler |
| JP2014234935A (en) * | 2013-05-31 | 2014-12-15 | 株式会社タクマ | Circulating fluidized bed boiler |
| JP2015081203A (en) * | 2013-10-21 | 2015-04-27 | 三菱日立パワーシステムズ株式会社 | Chemical looping combustion system |
| CN104848207A (en) * | 2015-04-07 | 2015-08-19 | 东南大学 | Chemical looping combustion device for solid fuel grading oxidation and method thereof |
| CN106247323A (en) * | 2016-09-14 | 2016-12-21 | 东南大学 | A kind of chemical chain combustion apparatus based on tower bubbling fluidized bed fuel reactor and method thereof |
| CN211667810U (en) * | 2019-12-20 | 2020-10-13 | 东方电气集团东方锅炉股份有限公司 | Chemical chain reaction device with wide load regulation capacity |
Non-Patent Citations (2)
| Title |
|---|
| 10 kW_(th)级串行流化床中木屑化学链燃烧试验;吴家桦;沈来宏;肖军;王雷;郝建刚;;化工学报;20090815(08);全文 * |
| 3 MW_(th)化学链燃烧装置设计方法;李振山;成茂;陈虎;蔡宁生;李维成;岳鹏飞;;新能源进展;20180710(03);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110953578A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101699187B (en) | Coal combustion apparatus capable of separating carbon dioxide and separation method thereof | |
| CN101245264B (en) | Single-bed self-heating type thermal decomposition gasification combustion reactor and thermal decomposition gasification combustion method | |
| CN105222129B (en) | A kind of coal-fired burning chemistry chains separation CO for coupling pure oxygen gasification2Method | |
| CN103667571B (en) | System and method of fluidized direct reduction of iron ore concentrate powder | |
| CN106554826B (en) | Circulating fluidized bed coal gasification method and device with fine ash fusion | |
| EA032282B1 (en) | Oxycombustion in a transport oxy-combustor | |
| KR101458872B1 (en) | Chemical looping combustion method and apparatus for solid fuels using different oxygen carriers | |
| CN107043641B (en) | Coal gasification method and device of circulating fluidized bed with fine ash return | |
| CN201241071Y (en) | Single-bed self-heating type thermal decomposition gasification combusting reactor | |
| CN102798222A (en) | Chemical-looping combustion device based on solid fuel and use method thereof | |
| CN109297015B (en) | Coupling pressurization oxygen-enriched combustion device of circulating fluidized bed/bubbling fluidized bed | |
| CN208649244U (en) | A kind of circulation fluidized bed coal gasifying system | |
| CN211667810U (en) | Chemical chain reaction device with wide load regulation capacity | |
| CN110953578B (en) | Chemical chain reaction device with wide load regulation capability and control method thereof | |
| CN102798221A (en) | Chemical-looping combustion device and use method thereof | |
| US4470254A (en) | Process and apparatus for coal combustion | |
| CN110205164A (en) | Circulating fluidized bed gasification device and ciculation fluidized bed gasification method | |
| KR101325095B1 (en) | Chemical-looping combustor for solid fuels | |
| KR102413872B1 (en) | Energy circulation system using circulating fluidized bed boiler and renewable energy | |
| CN112824502B (en) | Circulating fluidized bed gasification device and circulating fluidized bed gasification method | |
| CN201569172U (en) | Coal-firing device capable of separating carbon dioxide | |
| CN100393852C (en) | Fluidized bed pump-out gas deoxidation and equipment thereof | |
| CN221714253U (en) | Circulating combustion energy-saving system of coal-fired boiler | |
| CN114774141B (en) | Coke cooling method and system | |
| US20240116757A1 (en) | Methods for chemical process heating with carbon capture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |