CN109439369B - Coal-based chemical chain gasification method - Google Patents
Coal-based chemical chain gasification method Download PDFInfo
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- 238000002309 gasification Methods 0.000 title claims abstract description 133
- 239000003245 coal Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 title claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 135
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 135
- 239000001301 oxygen Substances 0.000 claims abstract description 135
- 239000007790 solid phase Substances 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 230000008929 regeneration Effects 0.000 claims abstract description 25
- 238000011069 regeneration method Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000012071 phase Substances 0.000 claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910005507 FeWO4 Inorganic materials 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000010883 coal ash Substances 0.000 description 5
- 229910052595 hematite Inorganic materials 0.000 description 5
- 239000011019 hematite Substances 0.000 description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 5
- 239000004449 solid propellant Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- -1 comprising Fe Chemical compound 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- AHIVCQLQCIBVOS-UHFFFAOYSA-N [Fe].[W] Chemical compound [Fe].[W] AHIVCQLQCIBVOS-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The embodiment of the invention discloses a coal-based chemical looping gasification method, which relates to the technical field of coal gasification, and improves the selectivity of synthesis gas by expanding the temperature interval of oxygen supply of an oxygen carrier and uniformly and dispersedly supplying oxygen for coal gasification in a larger temperature interval. The coal-based chemical looping gasification method comprises the steps of adding coal, an oxygen carrier containing tungstoferrite and a gasifying agent into a gasification reactor, and enabling the coal, the oxygen carrier and the gasifying agent to generate gasification reaction to generate a gas-phase product containing synthesis gas and a solid-phase product containing a reduced-state oxygen carrier; conveying at least one part of the solid-phase product to a regeneration reactor for oxidation treatment to obtain an oxidation state oxygen carrier; and returning the oxidation state oxygen carrier to the gasification reactor for gasification reaction. The coal-based chemical looping gasification method provided by the embodiment of the invention is suitable for a coal gasification process.
Description
Technical Field
The invention relates to the technical field of coal gasification, in particular to a carbon-based chemical chain gasification method.
Background
With the continuous development of scientific technology, the related technical personnel propose a novel chemical-looping gasification technology capable of cleanly and efficiently utilizing solid fuel, wherein the chemical-looping gasification technology is to add metal oxide into the solid fuel to utilize the metal oxide as an oxygen carrier, so that in the process of fuel gasification, lattice oxygen in the oxygen carrier can be used for replacing molecular oxygen, oxygen required by fuel gasification can be provided for the solid fuel, and a target product can be obtained by controlling the ratio of the lattice oxygen to the solid fuel. For example, the target products to be obtained by coal-based chemical looping gasification technology include CO (carbon monoxide) and H2(hydrogen) synthesis gas.
However, at present, when a target product is obtained by gasifying a solid fuel by a coal-based chemical looping gasification technique, a case where the oxygen content supplied by a metal or nonmetal oxide is high often occurs, and in this case, CO and H are easily caused2Respectively converted into CO2(carbon dioxide) and H2O (water), which in turn leads to the content of active constituents (i.e. CO and H) in the synthesis gas obtained2Content of (d) is low and the selectivity of the synthesis gas is poor.
Disclosure of Invention
The embodiment of the invention aims to provide a coal-based chemical looping gasification method, which improves the selectivity of synthesis gas by expanding the temperature interval of oxygen supply of an oxygen carrier and uniformly and dispersedly supplying oxygen for coal gasification in a larger temperature interval.
In order to achieve the above purpose, the embodiment of the present invention provides the following technical solutions:
the embodiment of the invention provides a coal-based chemical looping gasification method, which comprises the following steps: adding coal, an oxygen carrier containing tungstoferrite and a gasifying agent into a gasification reactor, and carrying out gasification reaction on the coal, the oxygen carrier and the gasifying agent to generate a gas-phase product containing synthesis gas and a solid-phase product containing a reduced-state oxygen carrier; conveying at least one part of the solid-phase product to a regeneration reactor for oxidation treatment to obtain an oxidation state oxygen carrier; and returning the oxidation state oxygen carrier to the gasification reactor for gasification reaction.
Optionally, the coal-based chemical looping gasification method further includes: part of the solid phase product is withdrawn from the gasification reactor and tungsten oxides are separated from the withdrawn solid phase product.
Optionally, the mass of the extracted solid phase product accounts for 2% -20% of the total mass of the solid phase product generated in the gasification reactor.
Optionally, the temperature in the gasification reactor is 700-850 ℃.
Optionally, when the oxidized oxygen carrier is returned to the gasification reactor, the coal, the wustite and the gasification agent are continuously added into the gasification reactor.
Optionally, the mass ratio of the tungsten iron ore added into the gasification reactor to the oxidation state oxygen carrier returned to the gasification reactor is 1: 15-1: 5.
Optionally, the mass ratio of the carbon in the coal to the oxygen carrier is 1: 25-1: 5.
Optionally, the temperature in the regeneration reactor is 800-1100 ℃.
Optionally, the gasifying agent comprises superheated steam, and the mass ratio of the gasifying agent to carbon in the coal is 1: 5-2: 1.
Optionally, the particle size range of the coal is the same as the particle size range of the oxygen carrier.
According to the coal-based chemical looping gasification method provided by the embodiment of the invention, the oxygen carrier containing the tungstolite ore is added into the gasification reactor so as to utilize the main component FeWO in the tungstolite ore4(ferrous tungstate) provides the coal in the gasification reactor with the oxygen required for its gasification due to FeWO4The temperature range of the released oxygen is larger, and the released oxygen can be uniformly dispersed in the larger temperature range, so that the FeWO is enabled to be4Oxygen can be gradually released in the process of continuously increasing the temperature after entering the gasification reactor, and the oxygen can gradually react with the coal, so that the problem of excessive oxidation of the coal caused by more concentrated temperature range of the released oxygen of the conventional oxygen carrier is avoided, and the CO and H in the synthesis gas obtained by the gasification reaction can be effectively improved2The selectivity of the synthesis gas is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the embodiments of the invention and not to limit the embodiments of the invention unduly. In the drawings:
FIG. 1 is a schematic flow diagram of a coal-based chemical looping gasification method according to an embodiment of the present invention;
FIG. 2 is FeWO provided in the examples of the present invention4Schematic representation of the presence at different temperatures.
Detailed Description
For the convenience of understanding, the technical solutions provided by the embodiments of the present invention are described in detail below with reference to the drawings of the specification. It is obvious that the described embodiments are only some, not all embodiments of the proposed solution. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention without any creative work belong to the protection scope of the embodiments of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a coal-based chemical looping gasification method, including:
step S1: adding coal, an oxygen carrier containing tungstoferrite and a gasifying agent into a gasification reactor, and carrying out gasification reaction on the coal, the oxygen carrier and the gasifying agent to generate a gas-phase product containing synthesis gas and a solid-phase product containing a reduced-state oxygen carrier.
Step S2: at least one part of the solid phase product is conveyed to a regeneration reactor for oxidation treatment, and an oxidation state oxygen carrier is obtained.
Step S3: and returning the oxidation state oxygen carrier to the gasification reactor for gasification reaction.
The above-mentioned wolframite ore contains FeWO as a main component4The ferro-tungsten ore is produced after reduction reaction and mainly comprises Fe (iron), W (tungsten) and WO2(tungsten dioxide) and FeO (ferrous oxide), wherein the reduced oxygen carrier can be converted into FeWO again after oxidation treatment in a regeneration reactor4And forming an oxidation state oxygen carrier. Thus, after the oxygen carrier in the oxidized state is recycled to the gasification reactor, the oxygen carrier comprising wustite contains oxidized oxygen carrier delivered from the regeneration reactor in addition to wustite.
The gasifying agent may be superheated steam. When coal, oxygen carrier and gasifying agent are used for gasification reaction, the generated products comprise gas-phase products and solid-phase products, wherein the gas-phase products comprise CO and H as effective components2The solid phase product of the synthesis gas comprises semicoke, coal ash and other substances generated after coal gasification and a reduced oxygen carrier generated after the oxygen carrier is reduced.
The gasification reaction occurring in the gasification reactor is represented by equations (1) to (3):
C+H2O＝CO+H2 (1)
C+CO2＝2CO (2)
CO+H2+FeWO4＝CO2+H2O+Fe+WO2 (3)
FeWO4the gasification reaction is carried out in the form shown in FIG. 2 at different temperatures. As can be seen from FIG. 2, when FeWO4At a temperature below 600 ℃, FeWO4Will release a small amount of oxygen, mainly to contain FeWO4、FeO、WO2The stable form of Fe exists; when FeWO4At a temperature of 600-700 ℃, FeWO4Will release more oxygen, mainly to contain FeWO4、Fe、WO2FeO and W exist in a stable form; when FeWO4At a temperature above 800 ℃, FeWO4The absorbed energy is more, and further releases oxygen, mainly comprising Fe, W and WO2And FeO exists in a relatively stable form.
From this, it is understood that FeWO shows a temperature rise from low to high in a wide temperature range as shown in FIG. 24The chemical bond between oxygen and metal element can gradually absorb energy, and when the absorbed energy reaches the bond energy of the chemical bond, the chemical bond between oxygen and metal element is broken, and oxygen is gradually released, thus indicating that FeWO4The temperature range of the released oxygen is wider, and the oxygen is released more uniformly in the wider temperature range.
According to the coal-based chemical looping gasification method provided by the embodiment of the invention, the oxygen carrier containing the tungstolite ore is added into the gasification reactor so as to utilize the main component FeWO in the tungstolite ore4Providing the coal in the gasification reactor with the oxygen required for its gasification, due to FeWO4The temperature range of the released oxygen is wide, and the released oxygen can be uniformly dispersed in the wide temperature range, so that the FeWO is enabled4Oxygen can be gradually released in the process of continuously increasing the temperature after entering the gasification reactor, and the oxygen can gradually react with the coal, so that the problem of excessive oxidation of the coal caused by more concentrated temperature range of the released oxygen of the conventional oxygen carrier is avoided, and the CO and H in the synthesis gas obtained by the gasification reaction can be effectively improved2The selectivity of the synthesis gas is improved.
Exemplarily, Fe as a main component, respectively2O3The hematite ore and the main component of FeWO4The description will be given by taking the wolframite stone as an oxygen carrier. In order to accurately reflect that the coal-based chemical-looping gasification method provided by the embodiment of the invention can effectively improve the selectivity of the synthesis gas, the gasification reactions respectively carried out by utilizing hematite and wustite are carried out under the same reaction conditions. Illustratively, under the conditions that the temperature in the gasification reactor is 800 ℃ and the pressure in the gasification reactor is 1bar, the gasification reaction is carried out by using hematite and wustite, respectively, and the selectivity of the obtained synthesis gas is shown in table 1 below.
TABLE 1
As can be seen from table 1 above, under the conditions of different mass ratios of the oxygen carrier to the carbon in the coal, the content of the effective components in the syngas obtained by using wustite as the oxygen carrier is higher than the content of the effective components in the syngas obtained by using hematite as the oxygen carrier, that is, the selectivity of the syngas obtained by using wustite as the oxygen carrier is higher than the selectivity of the syngas obtained by using hematite as the oxygen carrier, which means that the coal-based chemical-looping gasification method provided by the embodiment of the present invention can effectively improve the selectivity of the syngas.
In some embodiments, when wustite is selected as the oxygen carrier, FeWO in wustite is generally selected as the oxygen carrier4The tungstonite with the mass fraction of more than 80 percent adopts the high-grade tungstonite as the oxygen carrier, so that the oxygen carrying capacity of the oxygen carrier per unit mass can be improved, and the oxygen carrier can provide oxygen required by gasification for more coal during gasification reaction, so that more coal can be subjected to gasification reaction, and further the yield of synthesis gas in the gasification reaction can be effectively improved.
In order to enable the gasification reaction in the gasification reactor to proceed efficiently, in some embodiments the particle size range of the coal is the same as the particle size range of the oxygen carrier. Illustratively, the particle size range of the coal is 400-800 μm, and the particle size range of the oxygen carrier is 400-800 μm, so that after the coal and the oxygen carrier with the same particle size range are added into the gasification reactor, the coal and the oxygen carrier can be sufficiently and uniformly mixed under the action of the gasification agent, oxygen released by the oxygen carrier can be uniformly distributed around the coal and uniformly gasified with the coal, and thus the content of effective components in the gasification reaction can be effectively increased.
It will be appreciated that the gasification agent will typically comprise superheated steam, which in this case both acts as a fluidising medium to enable substantially uniform mixing of the coal and oxygen carrier, and as a reactant to participate in the gasification reaction to provide the H (hydrogen) required in the synthesis gas. In order to avoid that the coal and the oxygen carrier are difficult to mix well due to the fact that the quality of the gasifying agent added into the gasification reactor is low, in some embodiments, the mass ratio of the gasifying agent added into the gasification reactor to the carbon in the coal added into the gasification reactor is generally 1: 5-2: 1, so that the coal and the oxygen carrier can be mixed uniformly, a good hydrogen-carbon ratio can be formed, and the synthetic gas with good carbon and hydrogen can be generated. Of course, the mass ratio of the gasifying agent to carbon in the coal may be set by itself according to actual needs, and this embodiment is not limited thereto.
It is worth mentioning that the temperature in the gasification reactor can be set to 700-850 ℃. Referring to FIG. 2, FeWO is shown at a temperature of 700-850 deg.C4Mainly comprises Fe and WO2FeO, W, and the components of the above-mentioned forms have slowly stabilized, while FeWO is present at temperatures above 850 DEG C4Mainly comprises Fe and WO2FeO, W, and the components of which are essentially unchanged, i.e. FeWO at temperatures above 850 DEG C4Oxygen is not released basically, so when the temperature in the gasification reactor is set to be 700-850 ℃, the carbon in the coal can be ensured to be well gasified, and FeWO can be fully utilized4So that FeWO4The oxygen in the water can be completely released.
It is understood that, in step S2, when the solid-phase product is conveyed to the regeneration reactor for oxidation treatment to obtain the oxidation state oxygen carrier, all the solid-phase product may be conveyed to the regeneration reactor for oxidation treatment, or a part of the solid-phase product in the solid-phase product may be conveyed to the regeneration reactor for oxidation treatment, which is not limited in the embodiment of the present invention.
When the oxidation treatment is carried out in the regeneration reactor, the pressure in the regeneration reactor can be kept within the range of 0.1-1 Mpa, air is used as a gasifying agent for the oxidation treatment, and at the moment, a reduction oxygen carrier in a solid-phase product and oxygen in the air undergo an oxidation-reduction reaction and are converted into FeWO4I.e. an oxygen carrier in an oxidized state; and semicoke in the solid-phase product is combusted with oxygen in the air to provide heat for the oxidation of the reduced-state oxygen carrier.
The oxidation reaction of the reduced oxygen carrier in the regeneration reactor is shown in equation (4):
Fe+W+2WO2+2FeO+3O2＝3FeWO4 (4)
it should be noted that, in order to ensure that the reduced oxygen carrier can be stably converted into the oxidized oxygen carrier in the oxidation process of the reduced oxygen carrier, the temperature in the regeneration reactor can be set to 800-1100 ℃, so that when the reduced oxygen carrier is subjected to oxidation treatment, the situation that Fe and FeO in the reduced oxygen carrier are converted into Fe due to too high temperature in the regeneration reactor can be avoided2O3In the case of (1), it is ensured that the oxidized oxygen carrier obtained after the oxidation treatment of the reduced oxygen carrier is still FeWO4Further, the oxygen carrier in an oxidation state formed by converting the oxygen carrier in a reduction state can be effectively ensured to balance the supply amount of oxygen in the gasification reaction, and the selectivity of the synthetic gas is improved.
In some embodiments, the temperature in the gasification reactor is lower than the temperature in the regeneration reactor, which in turn causes the temperature of the solid phase product in the gasification reactor to be lower than the temperature in the regeneration reactor, and the solid phase product is heated after being transferred to the regeneration reactor. In order to fully utilize the heat released by the reaction occurring in the regeneration reactor, in some embodiments, the heat released by the burning of the semicoke in the regeneration reactor can be utilized to raise the temperature of the solid phase product, so that the waste of heat can be reduced, and the increase of economic cost caused by the temperature rise of the solid phase product by using other temperature rising devices can be avoided.
It should be noted that, when a part of the solid-phase product in the solid-phase product is conveyed to the regeneration reactor for oxidation treatment in step S2, the chemical-looping gasification method provided by the embodiment of the present invention further includes step S2': withdrawing a portion of the solid phase product from the gasification reactor and separating tungsten and tungsten oxides from the withdrawn solid phase product.
The solid phase product generated in the gasification reactor mainly comprises Fe, W and WO2FeO, semicoke, coal ash and the like, wherein W and WO are mentioned above2Has higher added value, thus the W and the WO are added2After separation from the solid phase product, W and WO can be used2The economic benefit brought by the method provided by the embodiment of the invention is improved, and the economic cost required by the method is effectively reduced.
Due to W and WO in the above substances2The density of (A) is higher than that of Fe, FeO, semicoke, coal ash and the like, so that when the above substances are separated, Fe, FeO, semicoke, coal ash and the like with lower density and W and WO with higher density can be separated by using a separation method such as air separation or gravity screening2Separating to obtain W and WO with high density and high added value2. In addition, W and WO are isolated2Since a small amount of Fe, FeO, semicoke, coal ash, etc. may be mixed in the reaction mixture, W and WO can be separated by a separation method such as temperature reduction or magnetic separation2Further separating to obtain W and WO with high purity2。
It can be understood that the solid phase product carries heat, so as to avoid taking away more heat from the gasification reactor when the solid phase product is extracted from the gasification reactor, in some embodiments, the mass of the extracted solid phase product may account for 2% to 20% of the total mass of the solid phase product generated in the gasification reactor, so that after the solid phase product is extracted from the gasification reactor, it is ensured that the gasification reactor still has sufficient heat, and that the gasification reaction in the gasification reactor still can be performed well.
It should be noted that after the reduced-state oxygen carrier is converted into the oxidized-state oxygen carrier, the oxidized-state oxygen carrier needs to be returned to the gasification reactor to continue the gasification reaction by using the oxidized-state oxygen carrier.
When the reduction-state oxygen carrier is subjected to oxidation treatment in the regeneration reactor, more heat can be absorbed, so that the oxidation-state oxygen carrier carries more heat, and after the oxidation-state oxygen carrier is returned to the gasification reactor, the oxidation-state oxygen carrier can be used for continuously providing oxygen required by gasification for the gasification reaction in the gasification reactor, and the heat carried by the oxidation-state oxygen carrier can be released in the gasification reactor, so that good heat circulation is formed between the gasification reactor and the regeneration reactor.
Because the oxygen carrier generates loss when circulating between the gasification reactor and the regeneration reactor, in order to compensate the loss of the oxygen carrier, when the oxidation state oxygen carrier is returned to the gasification reactor, the tungsten iron ore is also added into the gasification reactor, and the mass ratio of the tungsten iron ore added into the gasification reactor to the oxidation state oxygen carrier returned into the gasification reactor can be set to be 1: 15-1: 5, so that the oxygen released by the oxygen carrier added into the gasification reactor can be ensured to still be gasified with the coal in the gasification reactor while the oxidation state oxygen carrier is recycled, and the synthetic gas with high effective component content can be generated.
In some embodiments, when coal, a gasifying agent, and an oxygen carrier containing wustite and an oxygen carrier in an oxidized state are added to a gasification reactor, a mass ratio of carbon in the added coal to the added oxygen carrier may be set to 1:25 to 1: 5. Therefore, carbon in the coal can be uniformly gasified with oxygen released by the oxygen carrier, insufficient coal gasification caused by high carbon content in the coal is avoided, or carbon is excessively oxidized caused by low carbon content in the coal, and the content of effective components in the synthesis gas is reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and the present invention shall be covered thereby. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A coal-based chemical looping gasification method is characterized by comprising the following steps:
adding coal, an oxygen carrier containing tungstoferrite and a gasifying agent into a gasification reactor, and carrying out gasification reaction on the coal, the oxygen carrier and the gasifying agent to generate a gas-phase product containing synthesis gas and a solid-phase product containing a reduced-state oxygen carrier;
conveying at least one part of the solid-phase product to a regeneration reactor for oxidation treatment to obtain an oxidation state oxygen carrier;
returning the oxidized oxygen carrier to the gasification reactor for the gasification reaction;
wherein the temperature in the gasification reactor is 700-850 ℃.
2. The coal-based chemical looping gasification method according to claim 1, characterized by further comprising: withdrawing a portion of the solid phase product from the gasification reactor, and separating tungsten and tungsten oxides from the withdrawn solid phase product.
3. The coal-based chemical looping gasification method according to claim 2, characterized in that the mass of the solid phase product recovered accounts for 2-20% of the total mass of the solid phase product generated in the gasification reactor.
4. The coal-based chemical looping gasification method according to claim 1, characterized in that the coal, the wustite ore and the gasification agent are continuously added into the gasification reactor while the oxidation state oxygen carrier is returned to the gasification reactor.
5. The coal-based chemical looping gasification method according to claim 4, wherein the mass ratio of the wustite ore added to the gasification reactor to the oxidation state oxygen carrier returned to the gasification reactor is 1:15 to 1: 5.
6. The coal-based chemical looping gasification method according to claim 1, wherein the mass ratio of carbon in the coal to the oxygen carrier is 1: 25-1: 5.
7. The coal-based chemical looping gasification method according to claim 1, wherein the temperature in the regeneration reactor is 800-1100 ℃.
8. The coal-based chemical looping gasification method according to claim 1, wherein the gasifying agent comprises superheated steam, and the mass ratio of the gasifying agent to carbon in the coal is 1: 5-2: 1.
9. The coal-based chemical looping gasification method according to claim 1, characterized in that the particle size range of the coal is the same as the particle size range of the oxygen carrier.
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