CN113513751B - Chemical-looping combustion directional desulfurization process and device coupled with microwave technology - Google Patents

Chemical-looping combustion directional desulfurization process and device coupled with microwave technology Download PDF

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CN113513751B
CN113513751B CN202110342444.3A CN202110342444A CN113513751B CN 113513751 B CN113513751 B CN 113513751B CN 202110342444 A CN202110342444 A CN 202110342444A CN 113513751 B CN113513751 B CN 113513751B
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reactor
oxygen
fuel
deficient
sulfur
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CN113513751A (en
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罗明
董宇航
张海燕
覃艳军
周伦正
钱黎黎
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Jiangsu University
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00—Fluidised bed combustion apparatus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • C10L9/06—Treating solid fuels to improve their combustion by chemical means by oxidation
    • 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
    • F23C10/22—Fuel feeders specially adapted for fluidised bed combustion apparatus
    • 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
    • F23C10/26—Devices for removal of material from the bed combined with devices for partial reintroduction of material into the bed, e.g. after separation of agglomerated parts
    • 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
    • F23C10/28—Control devices specially adapted for fluidised bed, combustion apparatus
    • 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 
    • F23C2206/00—Fluidised bed combustion
    • F23C2206/10—Circulating fluidised bed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)

Abstract

The invention provides a chemical-looping combustion directional desulfurization process and a device for coupling microwave technology, wherein solid fuel is subjected to desulfurization reaction through microwave frequency, the desulfurized solid fuel enters a sufficient oxygen fuel reactor, and generated sulfur-containing gas is independently or mixed with a fluidization medium and then enters an oxygen-deficient fuel reactor; after the solid fuel after desulfurization and the fluidization medium entering the oxyfuel reactor are subjected to vaporization reaction, the solid fuel and the oxygen carrier are subjected to reduction reaction in the oxyfuel reactor; controlling the peroxy coefficient R in the oxygen-deficient fuel reactor by controlling the entering amount of oxygen carrier entering the oxygen-deficient fuel reactor; in the oxygen-deficient fuel reactor, the sulfur-containing gas and the unreacted oxygen carrier form metal sulfides, and the metal sulfides and the rest of the oxygen carrier restore the oxygen-deficient oxygen carrier to an oxygen carrier containing lattice oxygen in the air reactor. The invention realizes desulfurization from the source and ensures CO generated in the fuel reactor 2 No further desulfurization is required after the catalyst is trapped.

Description

Chemical-looping combustion directional desulfurization process and device coupled with microwave technology
Technical Field
The invention relates to the field of metallurgy or coal combustion desulfurization or environmental treatment, in particular to a chemical-looping combustion directional desulfurization process and device by a coupled microwave technology.
Background
With the rapid development of economy and the continuous progress of society, the energy consumption mainly based on fossil energy is continuously increased. However, the traditional fossil energy source causes serious damage to the environment in the process of production, transportation and utilization, and the main combustion product is CO 2 、SO x 、NO x And the like are the main fierces of the environmental problems such as the current greenhouse effect, acid rain and the like. Whereas the chemical looping combustion (Chemical Looping Combustion, CLC) technique divides the traditional combustion process into two steps by means of an Oxygen Carrier (OC), uses lattice Oxygen in the Oxygen carrier to oxidize the fuel, avoids direct contact of the fuel with air, thereby effectively suppressing thermal and rapid NO x Is generated; in addition, CO generated at the fuel reactor outlet 2 Not covered by N 2 Dilution is carried out without a separation device, thereby avoiding CO 2 The high energy consuming process required for separation. It follows that the CLC technique is a type with CO 2 Clean and efficient combustion technology with internal separation.
Although CLC technology can effectively inhibit NO x At the same time can also discharge CO 2 Trapping but not avoiding SO x Is formed and discharged. The sulfur content in the coal in China is greatly changed in a range of about 0.02 to 10.48 percent under the influence of geographical distribution and deposition environment. The reserved reserves of coal with sulfur content more than 2.00 percent account for 9.90 percent of the reserved reserves nationally. The medium-high sulfur coal and even the high sulfur coal can be effectively utilized, and the energy demand pressure of China can be relieved to a certain extent.
In the CLC process of coal, sulfur in the coal may have some influence on the reaction process. This is mainly reflected in: in the fuel reactor, sulfur may react with the oxygen carrier to form sulfur compounds, which affect the reactivity and stability of the oxygen carrier, while the gaseous sulfur species (e.g., H 2 S、SO x COS, etc.) will also contribute to the CO at the reactor outlet 2 Purity has an effect, especially when CO 2 Sulfur-containing gas (H) 2 S、SO x ) When the concentration of S is higher than 50ppm, the problems of S deposition on the surface, corrosion on the transported pipeline and the like can be caused, and CO is further influenced 2 Is transported and stored for use; in an air reactor, the sulfur-containing compounds generated in the oxygen carrier may further react with O in the air 2 React to form SO x Thereby causing damage to the environment.
Through early research on migration and conversion rules of sulfur in coal in CLC process, most of the coal is foundSulfur in (2) will be reacted with SO at the fuel reactor outlet 2 And H 2 S escapes in the form of SO at the air reactor outlet 2 In the form of (c) escape. Although some of the sulfur compounds may be removed by means of the added desulfurizing agent, the concentration of sulfur compounds in the gas phase at the outlet of the fuel reactor may still exceed 100ppm, thereby severely affecting CO 2 How to reduce CO in a fuel reactor, and the purity of the fuel reactor and its subsequent trapping and sequestering processes 2 The concentration of sulfur-containing gas in the furnace is a problem to be solved.
Disclosure of Invention
The invention provides a chemical-looping combustion directional desulfurization process and a device for coupling microwave technology, aiming at the defects in the prior art. On the one hand, desulfurization from the source is realized, and CO generated in the fuel reactor is realized 2 After being trapped, the catalyst meets the utilization and sealing conditions without further desulfurization; on the other hand, through the circulation of the oxygen carrier, the S element is directionally moved to the air reactor and released into sulfur-containing gas, so that the traditional desulfurization device can be used for removing sulfur-containing pollutants, the running cost is reduced, and the reliability is improved.
The present invention achieves the above technical object by the following means.
A chemical-looping combustion directional desulfurization process coupled with microwave technology comprises the following steps:
microwave desulfurization stage: mixing solid fuel with H 2 Adding the solid fuel into a microwave reactor, carrying out desulfurization reaction on the solid fuel through microwave frequency, enabling the desulfurized solid fuel to enter a sufficient oxygen fuel reactor, and enabling the generated sulfur-containing gas to enter an oxygen-deficient fuel reactor independently or after being mixed with a fluidization medium;
chemical looping combustion phase: the desulfurized solid fuel is vaporized with the fluidizing medium entering the oxyfuel reactor and then is carried out with the oxygen carrierCarrying out reduction reaction in a foot oxygen fuel reactor; part of unreacted and reacted oxygen carrier enters the oxygen-deficient fuel reactor through a regulating valve, and the peroxy coefficient R in the oxygen-deficient fuel reactor is controlled by controlling the entering amount of the oxygen carrier entering the oxygen-deficient fuel reactor; the rest oxygen carrier is input into an air reactor; high purity CO by a first cyclone 2 Separating from the oxyfuel reactor;
sulfur-containing gas fixing stage: in the oxygen-deficient fuel reactor, the sulfur-containing gas carried by the fluidizing medium and unreacted oxygen carrier generate metal sulfide, the fluidizing medium plays a role in fluidization, and the metal sulfide and the rest oxygen carrier enter an air reactor; separating the high temperature fluidizing medium from the oxygen-depleted fuel reactor by a second cyclone;
recovery of lattice oxygen and sulfur release phases: in the air reactor, the reacted oxygen carrier is reacted with air to restore the oxygen carrier with lattice oxygen; reacting the metal sulfide with air to generate an oxygen carrier and sulfur-containing gas; the oxygen carrier generated in the air reactor is input into a sufficient oxygen fuel reactor, and the sulfur-containing gas generated in the air reactor is separated by an AR cyclone separator.
Further, the microwave frequency of the microwave reactor is 1GHz, and the radiation duration is 30s.
Further, the temperature of the foot oxygen fuel reactor is 800-1200 ℃, and the peroxy coefficient R of the foot oxygen fuel reactor is 1.9-2.0.
Further, the temperature of the oxygen-deficient fuel reactor is 700-1000 ℃; and controlling the opening degree of the regulating valve by monitoring the concentration of the sulfur-containing gas at the inlet of the oxygen-deficient fuel reactor, so that the peroxy coefficient R in the oxygen-deficient fuel reactor is controlled to be 0.8-0.9.
Further, the temperature in the air reactor is 800-1250 ℃.
The device for the chemical looping combustion directional desulfurization process coupled with the microwave technology comprises a microwave reactor, an air reactor, a sufficient oxygen fuel reactor and an oxygen-deficient fuel reactor; the microwave reactor is communicated with the oxyfuel reactor through a desulfurization fuel conveying pipeline; the bottom of the oxygen-rich fuel reactor is communicated with the oxygen-poor fuel reactor through a fuel reactor connecting pipeline, and a regulating valve with a powder flowmeter is arranged on the fuel reactor connecting pipeline and is used for regulating the peroxy coefficient R in the oxygen-poor fuel reactor; the bottom of the oxyfuel reactor is provided with a fluidization medium inlet D; the bottom of the oxyfuel reactor is communicated with the air reactor through a first feed back pipe; the bottom of the oxygen-deficient fuel reactor is communicated with the air reactor through a second feed back pipe; the bottom of the oxygen-deficient fuel reactor is provided with a mixed fluidization medium inlet F; the air reactor is communicated with the AR cyclone separator through an air reactor riser, and the AR cyclone separator is communicated with the foot oxygen fuel reactor through an AR cyclone separator dipleg.
Further, air distribution plates are arranged at the lower parts of the air reactor, the oxygen-rich fuel reactor and the oxygen-poor fuel reactor.
Further, a first cyclone separator is arranged at the upper part of the oxyfuel reactor, and high-purity CO is arranged on the first cyclone separator 2 The outlet E is communicated with the oxyfuel reactor through a dipleg of the first cyclone separator and is used for returning part of unreacted solid fuel and oxygen carrier to the oxyfuel reactor;
the upper part of the oxygen-deficient fuel reactor is provided with a second cyclone separator, the second cyclone separator is provided with a high-temperature fluidization medium outlet H, and the second cyclone separator is communicated with the oxygen-deficient fuel reactor through a second cyclone separator dipleg and is used for returning separated solid particles to the oxygen-deficient fuel reactor.
The invention has the beneficial effects that:
1. the invention relates to a chemical-looping combustion directional desulfurization process of a coupled microwave technology, which is characterized in that a microwave reactor is added, and about 70% of S in a solid fuel is in a gaseous state H under specific conditions 2 S-type separation obviously reduces the concentration of sulfur-containing gas at the outlet of the oxyfuel reactor, effectively ensures CO 2 And the subsequent transport and storage processes, and reduces the amount of desulfurizing agent (limeStone, mica stone, etc.).
2. The invention relates to a chemical looping combustion directional desulfurization process of a coupling microwave technology, which is characterized in that a first flue gas analyzer and a second flue gas analyzer are respectively arranged at an inlet and an outlet of an oxygen-deficient fuel reactor and used for monitoring the concentration of gas in real time, the first flue gas analyzer is associated with a regulating valve, the regulating valve is changed when the concentration is changed, and the opening degree of the regulating valve is also increased when the concentration of sulfur-containing gas is increased, so that the circulation amount of an oxygen carrier in the oxygen-deficient fuel reactor is controlled, the lower peroxy coefficient R in the oxygen-deficient fuel reactor is ensured, and the oxygen carrier is easier to react with sulfur-containing gas (H under the condition 2 S、COS、CS 2 Etc.) to produce metal sulfides, directionally migrating through the return line into the air reactor where S in the metal sulfides is oxidized to SO 2 The directional desulfurization effect can be achieved only by installing a set of traditional desulfurization device at the tail part of the air reactor.
3. The oxygen carrier is used for chemical looping combustion oxygen supply in the oxygen-rich fuel reactor on one hand, and reacts with S-containing gas in the oxygen-poor fuel reactor on the other hand, so that the purpose of fixing S element is achieved, S element is released after the oxygen carrier is directionally migrated to the air reactor, and the CO trapped by the S-containing gas is reduced 2 The influence of the purity of the sulfur removal device on the S element is fully utilized.
4. The invention relates to a chemical-looping combustion directional desulfurization process of a coupled microwave technology, which is used for removing part of S in coal by a microwave reactor; the oxyfuel reactor receives the coal from which part S is removed, and burns to release heat, thus obtaining low-sulfur CO 2 A gas; the oxygen-deficient fuel reactor receives the S-containing gas separated out by the microwave reactor, and generates metal sulfide through reaction with an oxygen carrier to fix S element; oxygen is supplied to the air reactor to restore lattice oxygen for the oxygen carrier, and the oxygen carrier reacts with metal sulfide to generate SO 2 SO is to be 2 Releasing and desulfurizing by using a tail desulfurizing device. Through the mutual cooperation of the main components, the S element is converted into a solid state from a gas state, directionally migrates to the air reactor and then is converted back into the gas state, so that the subsequent removal work is facilitated.
Drawings
FIG. 1 is a schematic diagram of a chemical looping combustion directional desulfurization device coupled with microwave technology according to the invention.
FIG. 2a is a graph showing the concentration profile of sulfur-containing gas at the outlet of a conventional copper-based oxygen carrier reactor under different peroxy coefficient R schemes.
FIG. 2b is a graph showing the concentration profile of sulfur-containing gas at the outlet of a foot-oxygen reactor for copper-based oxygen carriers of the present invention under different peroxy coefficient R schemes.
FIG. 3a is a graph showing the concentration profile of sulfur-containing gas at the outlet of a foot-oxygen reactor for a prior art nickel-based oxygen carrier under different peroxy coefficient R schemes.
FIG. 3b is a graph showing the concentration profile of sulfur-containing gas at the outlet of the oxygen reactor for nickel-based oxygen carriers of the present invention under different peroxy coefficient R schemes.
FIG. 4 is a flow chart of a chemical looping combustion directional desulfurization process of the coupled microwave technology of the invention.
FIG. 5 is a graph showing the product distribution at different peroxy coefficients R in a lean oxygen fuel reactor under a copper-based oxygen carrier according to the invention.
In the figure:
1-a microwave reactor; 2-desulphurized fuel delivery conduit; a 3-foot oxy-fuel reactor; 4-a first air distribution plate; a 5-fuel reactor connecting line; 6-a first feed back pipe; 7-a regulating valve; an 8-oxygen-lean fuel reactor; 9-a second air distribution plate; 10-a first flue gas analyzer; 11-AR air distribution plate; 12-a second feed back pipe; 13-an air reactor; 14-a second cyclone leg; 15-a second cyclone; 16-a second flue gas analyzer; 17-a first cyclone leg; 18-a first cyclone; 19-an air reactor riser; 20-a third flue gas analyzer; 21-AR cyclone dipleg; 22-AR spin separator; a-a solid fuel feed inlet; B-H 2 An air inlet; a C-sulfur-containing gas outlet; d-a fluidization medium inlet; e-high purity CO 2 An outlet; f-mixing a fluidization medium inlet; g-oxygen carrier inlet; h-high temperature fluidization medium outlet; i-a slag discharge port; j-air inlet; k-sulfur-containing and oxygen-deficient hot flue gas outlet.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "axial," "radial," "vertical," "horizontal," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
As shown in fig. 1, the present inventionThe invention relates to a device for directional desulfurization by chemical looping combustion of a coupled microwave technology, which comprises a microwave reactor 1, an air reactor 13, a sufficient oxygen fuel reactor 3 and an oxygen-deficient fuel reactor 8; the microwave reactor 1 is respectively provided with a solid fuel feed inlet A, H 2 A gas inlet B and a sulfur-containing gas outlet C; the microwave reactor 1 is communicated with the oxyfuel reactor 3 through a desulfurization fuel conveying pipeline 2; the inside of the oxyfuel reactor 3 is provided with a first air distribution plate 4, the bottom of the oxyfuel reactor 3 is provided with a fluidization medium inlet D, the upper part of the oxyfuel reactor 3 is provided with a first cyclone separator 18, and the first cyclone separator 18 is provided with high-purity CO 2 Outlet E of the high purity CO 2 A third flue gas analyzer 20 is arranged at the outlet E, and the first cyclone separator 18 is communicated with the oxyfuel reactor 3 through a first cyclone separator dipleg 17 and is used for returning part of unreacted solid fuel and oxygen carrier to the oxyfuel reactor 3; the bottom of the oxyfuel reactor 3 is communicated with an oxygen-deficient fuel reactor 8 through a fuel reactor connecting pipeline 5, and a regulating valve 7 is arranged on the fuel reactor connecting pipeline 5 and is used for regulating the peroxy coefficient R in the oxygen-deficient fuel reactor 8; the bottom of the oxyfuel reactor 3 is communicated with an air reactor 13 through a first feed back pipe 6; the oxygen-deficient fuel reactor 8 is internally provided with a second air distribution plate 9, the bottom of the oxygen-deficient fuel reactor 3 is provided with a mixed fluidization medium inlet F, the mixed fluidization medium inlet F is used for entering mixed gas of fluidization medium and sulfur-containing gas, and a first flue gas analyzer 10 is arranged at the mixed inlet F and is used for detecting the sulfur concentration in the fluidization medium and the sulfur-containing gas; the upper part of the oxyfuel reactor 3 is also provided with an oxygen carrier inlet G for supplementing an oxygen carrier. The upper part of the oxygen-deficient fuel reactor 8 is provided with a second cyclone separator 15, the second cyclone separator 15 is provided with a high-temperature fluidization medium outlet H, and a second flue gas analyzer 16 is arranged at the high-temperature fluidization medium outlet H and is used for monitoring the concentration of sulfur-containing gas at the outlet of the oxygen-deficient fuel reactor 8; the second cyclone 15 communicates with the oxygen-lean fuel reactor 8 via a second cyclone dipleg 14 for returning separated solid particles to the oxyfuel reactor 3. The bottom of the oxygen-deficient fuel reactor 8 passes through a second feed back pipe12 are communicated with an air reactor 13; the bottom of the oxygen-deficient fuel reactor 8 is provided with a slag discharge port I; an AR air distribution plate 11 is arranged in the air reactor 13, an air inlet J is formed in the bottom of the air reactor 13, the air reactor 13 is communicated with an AR cyclone separator 22 through an air reactor lifting pipe 19, and the AR cyclone separator 19 is communicated with the oxyfuel reactor 3 through an AR cyclone separator dipleg 21. The AR cyclone separator 21 is provided with a sulfur-containing and oxygen-deficient hot flue gas outlet K.
Example 1
Oxygen carrier of chemical chain combustion is selected to synthesize oxygen carrier, copper-based oxygen carrier is prepared by dipping method to prepare CuO/SiO 2 Wherein CuO/SiO 2 The mass ratio of (2) is 50:50. the solid fuel adopts Xinzhou coal, and the fluidizing medium adopts water vapor and CO 2 Is a mixed gas of (a) and (b). Table 1 shows the industrial analysis and elemental analysis of Xinzhou coal.
TABLE 1 Industrial analysis and elemental analysis of Xinzhou coal
The inorganic sulfur content in coal is high, and sulfate sulfur is not easy to decompose at high temperature, especially calcium sulfate. About 10% of the sulfur in the coal is present as sulfate sulfur and does not participate in the reaction.
For prior art chemical chain double circulation fluidized beds:
firstly, related functions of the microwave heater 1 are closed, the regulating valve 7 and the second feed back pipe 12 are closed, the traditional chemical chain double-circulation fluidized bed is simulated by using other components, new oxygen carrier, desulfurizing agent and solid fuel enter the reactor from the solid fuel inlet A, the temperature in the oxyfuel reactor 3 is set to 800-1200 ℃, the peroxy coefficient R is controlled to be about 2.0, the temperature of the air reactor 13 is set to 800-1250 ℃, and the reactor is operated under the condition that the tail CO 2 Collecting SO 2 As shown in FIG. 2a, the concentration of S in the gas is 195.24ppm, higher than that of CO 2 The required concentration for the subsequent trapping and sequestering processes. Changing the peroxy coefficient R in the fuel reactor, the remaining conditions being unchanged, monitoringTail CO measurement 2 Collecting SO 2 As shown in fig. 2a, the S concentration exceeds the standard. Wherein the main reactions occurring in the fuel reactor are as follows:
2.153C 58.6833 H 31.75 S 0.91875 (H 2 O) 6.2361 (N 2 ) 0.9287 +291.658CuO＝
291.658Cu+126.757CO 2 +47.615H 2 O+1.978SO 2 +1.464N 2
while the residual conditions are unchanged even if the peroxy coefficient R in the oxyfuel reactor is changed, the tail CO is monitored 2 Collecting SO 2 As shown in fig. 2a, the S concentration exceeds the standard.
The invention relates to a chemical-looping combustion directional desulfurization process by a coupled microwave technology, which comprises the following steps of:
microwave desulfurization stage: in the microwave reactor 1, H 2 From H 2 The air inlet B is arranged, coal is added from the solid fuel feed inlet A, the microwave frequency is 1GHz, the radiation time is 30S, and S element and H element in the coal 2 Reaction to produce H 2 S, the desulfurized coal enters a oxyfuel reactor 3 through a desulfurized fuel conveying pipeline 2, and the pulverized coal is pyrolyzed by a microwave reactor and then is treated with sulfur-containing synthesis gas (H) 2 、CO、CO 2 、H 2 O、N 2 And H 2 S) escapes into the oxygen-depleted reactor, H in the synthesis gas 2 、CO、CO 2 、H 2 O and N 2 The respective ratios were 45%, 32%, 10% and 3%. The sulfur-containing synthesis gas accounts for 40% of the total mass of the pulverized coal, H 2 S is present in very small amounts in the synthesis gas, but H 2 S accounts for 70% of total sulfur. The sulfur-containing synthesis gas is transported and mixed with the fluidizing medium and then introduced into the bottom of the oxygen-lean fuel reactor 8 from the fluidizing medium and sulfur-containing gas mixing inlet F.
Coal chemical looping combustion stage: in the oxyfuel reactor 3, the oxyfuel reactor 3 is a bubbling bed, the temperature is set to 800-1200 ℃, the desulfurized coal enters the oxyfuel reactor 3 from the desulfurized fuel conveying pipeline 2, and is mixed with oxygen carrier from the air reactor 13 in the oxyfuel reactor 3, and flows downwardsThe chemical gas (generally, water vapor and carbon dioxide) is introduced into the bottom of the oxyfuel reactor 3 from the fluidization medium inlet D, the peroxy coefficient R in the oxyfuel reactor 3 is controlled to be about 2.0, the solid fuel and the oxygen carrier undergo a reduction reaction, oxygen in the reduction reaction comes from lattice oxygen in the solid heat carrier, and the oxygen carrier is reduced. A first cyclone 18 is arranged at the upper part of the oxyfuel reactor 3, and the generated gas is extracted from high-purity CO 2 Outlet E leaves, and high-purity CO is obtained after condensation and water removal 2 . Part of the unreacted solid fuel and the reacted and unreacted oxygen carrier are returned from the first cyclone leg 17 to the oxyfuel reactor 3 to continue to participate in the reaction. After the reaction is finished, the oxygen carrier is migrated from the upper oxygen-rich fuel reactor 3 to the lower oxygen-poor fuel reactor 8 through the fuel reactor connecting pipeline 5, the fuel reactor connecting pipeline 5 is provided with a regulating valve 7, and the circulating amount of the oxygen carrier in the oxygen-poor fuel reactor 8 is controlled through the regulating valve 7, so that the oxygen-poor fuel reactor 8 is ensured to have a lower peroxy coefficient R, the redundant oxygen carrier directly returns to the air reactor 13 through the first feed back pipe 6 at one side of the fuel reactor connecting pipeline 5, and the main reaction in the oxygen-rich fuel reactor 3 is as follows:
5.442C 35.21 H 19.05 S 0.18375 (H 2 O) 3.741 (N 2 ) 0.557 +437.075CuO＝
437.075Cu+191.619CO 2 +72.196H 2 O+SO 2 +1.516N 2
sulfur-containing gas fixing stage: in the oxygen-deficient fuel reactor 8, the oxygen-deficient fuel reactor 8 is a bubbling bed, the temperature is set to 700-1000 ℃, the reaction and unreacted oxygen carrier enter the oxygen-deficient fuel reactor 8 from the upper part through a fuel reactor connecting pipeline 5, a first flue gas analyzer 10 and a second flue gas analyzer 16 are respectively arranged at the inlet and the outlet of the oxygen-deficient reactor 8, the concentration of sulfur-containing gas in a mixed gas inlet F of the oxygen-deficient reactor 8 and the concentration of sulfur-containing gas in a high-temperature fluidization medium outlet H of the oxygen-deficient fuel reactor 8 are monitored, the first flue gas analyzer 10 is associated with a regulating valve 7, the excess coefficient corresponding to the gas under different concentrations is fed back to the regulating valve 7 through calculation, and two combustion gases are controlledThe opening of a regulating valve 7 on a connecting pipeline between the material reactors is controlled, so that the circulation quantity of oxygen carriers is controlled, the regulating valve 7 drops the oxygen carriers with the corresponding excess coefficient of 0.8-0.9 of sulfur-containing synthetic gas at the outlet of the microwave reactor 1 into the oxygen-deficient reactor, and the distribution of products under different peroxy coefficients R is shown in figure 5. At the current peroxy coefficient R of 0.8-0.9, H in the sulfur-containing gas 2 S gas and unreacted oxygen carrier are liable to react to form copper sulfide (typically Cu 2 S, cuS), sulfur-containing gas and fluidizing gas (CO) 2 ) Introducing new oxygen carrier from the oxygen carrier inlet G into the bottom of the oxygen-deficient fuel reactor 8 from the mixed inlet F of the fluidizing medium and sulfur-containing gas, and then reacting with the sulfur-containing gas carried in by the fluidizing medium, wherein copper sulfide (Cu 2 S, cuS) and reacted and unreacted oxygen carrier are returned from the second feed back pipe 12 to the air reactor 13. The upper part of the oxygen-deficient fuel reactor 8 is provided with a second cyclone separator 15, the separated solid particles return to the oxygen-deficient fuel reactor 8 from the lower material leg 14 to continue to participate in the reaction, the high-temperature fluidization medium leaves from the high-temperature fluidization medium outlet H, the gas is basically free of gaseous S, and the gas is introduced into the oxygen-deficient fuel reactor 8 from F again after being treated. The solid residue is discharged from a slag discharging port I at the bottom. The main reactions taking place in the oxygen-depleted fuel reactor 8 are as follows: (sulfur-containing gas in the form of H) 2 S example
2CuO+H 2 S(g)+H 2 (g)＝Cu 2 S+2H 2 O(g)
H 2 S(g)+CuO＝CuS+H 2 O(g)
Restoring the lattice oxygen release sulfur phase: in the air reactor 13, the temperature in the air reactor 13 is set to 800-1250 c,
the copper sulphide and the oxygen carrier react with the air J introduced from the bottom of the air reactor 13, on the one hand the oxygen carrier losing oxygen reverts to lattice oxygen, and on the other hand the oxidation reaction with the copper sulphide takes place, SO that the copper sulphide reverts to the oxygen carrier and releases sulphur-containing gas, mainly SO 2 . Separated by an AR cyclone separator 22 at the upper part after passing through an air reactor riser 19, and the oxygen-depleted and sulfur-containing gas leaves through a sulfur-containing and oxygen-depleted hot flue gas outlet K and is then desulfurized by a conventional desulfurization device, so that the obtained solid oxygen carrier particles are introducedThe AR cyclone leg 21 is fed to the oxyfuel reactor 3 for reaction with solid fuel. A round of the cycle is completed. The main reactions taking place in the air reactor 13 are as follows:
2Cu+O 2 (g)＝2CuO
Cu 2 S+2O 2 (g)＝2CuO+SO 2 (g)
2CuS+3O 2 (g)＝2CuO+2SO 2 (g)
monitoring of the device tail CO with a third flue gas analyzer 20 2 Collecting SO 2 The concentration of (2) is shown in FIG. 2b, where the sulfur concentration in the collected gas is 49.10ppm, which is less than the desired 50ppm. Changing the peroxy coefficient R in the oxyfuel reactor, keeping the other conditions unchanged, and monitoring the tail CO 2 Collecting SO 2 As shown in fig. 2b, the S concentration is satisfactory.
Example 2
Prior art chemical chain double circulation fluidized bed:
preparation of oxygen carrier NiO/Al by impregnation method using nickel-based oxygen carrier 2 O 3 Wherein NiO/Al 2 O 3 The mass ratio of (2) is 40:60. other conditions are unchanged, and the tail CO of the device and the traditional chemical chain double-circulation fluidized bed after the improvement of the invention is obtained by monitoring 2 Collecting SO 2 As shown in fig. 3 a. The main reactions taking place in a conventional chemical-looping dual-circulation fluidized bed with a peroxy coefficient r=2.0 in the fuel reactor are as follows:
2.092C 58.6833 H 31.75 S 0.478125 (H 2 O) 6.2361 (N 2 ) 0.7 +280.675NiO(s)＝
280.675Ni(s)+122.736CO 2 +46.245H 2 O+SO 2 +1.464N 2
the sulfur gas concentration at the fuel reactor outlet was 145.70ppm. Changing the peroxy coefficient R in the fuel reactor, keeping the other conditions unchanged, and monitoring the tail CO 2 Collecting SO 2 As shown in fig. 3a, the S concentration exceeds the standard.
The invention relates to a chemical-looping combustion directional desulfurization process by a microwave coupling technology, which comprises the following steps:
preparation of oxygen carrier NiO/Al by impregnation method using nickel-based oxygen carrier 2 O 3 Wherein NiO/Al 2 O 3 The mass ratio of (2) is 40:60. other conditions are unchanged, and the tail CO of the device and the traditional chemical chain double-circulation fluidized bed after the improvement of the invention is obtained by monitoring 2 Collecting SO 2 As shown in fig. 3 b. When the peroxy coefficient r=2.0 in the oxyfuel reactor in this device, the main reactions taking place therein are as follows:
10.458C 58.6833 H 31.75 S 0.095625 (H 2 O) 6.2361 (N 2 ) 0.7 +1395.376NiO＝
1395.376Ni+613.682CO 2 +231.227H 2 O+SO 2 +7.32N 2
the sulfur-containing gas concentration at the outlet of the oxyfuel reactor was 48.06ppm. Changing the peroxy coefficient R in the oxyfuel reactor, keeping the other conditions unchanged, and monitoring the tail CO 2 Collecting SO 2 As shown in fig. 3b, the S concentration is satisfactory.
By combining the above embodiments, compared with the prior art, the invention has the advantages that the S element in the tail gas can be reduced by 67% after the process flow of the invention is adopted, and the effect is obvious.
It should be understood that although the present disclosure has been described in terms of various embodiments, not every embodiment is provided with a separate technical solution, and this description is for clarity only, and those skilled in the art should consider the disclosure as a whole, and the technical solutions in the various embodiments may be combined appropriately to form other embodiments that will be understood by those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.

Claims (8)

1. The chemical-looping combustion directional desulfurization process coupled with the microwave technology is characterized by comprising the following steps of:
microwave desulfurization stage: mixing solid fuel with H 2 Adding the sulfur-containing gas into a microwave reactor (1), carrying out desulfurization reaction on the solid fuel through microwave frequency, enabling the desulfurized solid fuel to enter a sufficient oxygen fuel reactor (3), and enabling the generated sulfur-containing gas to enter an oxygen-deficient fuel reactor (8) after being singly mixed with a fluidization medium or being mixed with the fluidization medium;
chemical looping combustion phase: the desulfurized solid fuel and the fluidized medium entering the oxyfuel reactor (3) are subjected to vaporization reaction and then are subjected to reduction reaction with an oxygen carrier in the oxyfuel reactor (3); part of unreacted and reacted oxygen carrier enters the oxygen-deficient fuel reactor (8) through the regulating valve (7), and the peroxy coefficient R in the oxygen-deficient fuel reactor (8) is controlled by controlling the entering amount of the oxygen carrier entering the oxygen-deficient fuel reactor (8); the rest oxygen carrier is input into an air reactor (13); high purity CO is separated by a first cyclone (18) 2 Separating from the oxyfuel reactor (3);
sulfur-containing gas fixing stage: in the oxygen-deficient fuel reactor (8), the fluidization medium carries the entering sulfur-containing gas and unreacted oxygen carrier to generate metal sulfide, and the metal sulfide and the rest oxygen carrier enter an air reactor (13); separating the high temperature fluidizing medium from the oxygen-depleted fuel reactor (8) by means of a second cyclone (15);
recovery of lattice oxygen and sulfur release phases: in the air reactor (13), the reacted oxygen carrier is reacted with air to restore the oxygen carrier with lattice oxygen; reacting the metal sulfide with air to generate an oxygen carrier and sulfur-containing gas; the oxygen carrier generated in the air reactor (13) is input into the oxyfuel reactor (3), and the sulfur-containing gas generated in the air reactor (13) is separated by an AR cyclone separator (22).
2. The chemical looping combustion directional desulfurization process coupled with microwave technology according to claim 1, characterized in that the microwave frequency of the microwave reactor (1) is 1GHz and the radiation duration is 30s.
3. The process for directional desulfurization by chemical looping combustion coupled with microwave technology according to claim 1, characterized in that the temperature of said reactor (3) for oxyfuel is 800-1200 ℃, and the peroxy coefficient R of said reactor (3) for oxyfuel is 1.9-2.0.
4. The microwave technology coupled chemical looping combustion directed desulfurization process according to claim 1, characterized in that the temperature of the oxygen-depleted fuel reactor (8) is 700-1000 ℃; the opening degree of the regulating valve (7) is controlled by monitoring the concentration of sulfur-containing gas in the fluidizing medium entering the oxygen-deficient fuel reactor (8), so that the peroxy coefficient R in the oxygen-deficient fuel reactor (8) is controlled to be 0.8-0.9.
5. The process for the directed desulfurization by chemical looping combustion coupled with microwave technology according to claim 1, characterized in that the temperature inside the air reactor (13) is 800-1250 ℃.
6. A device for a chemical looping combustion directed desulfurization process coupled to microwave technology according to claim 1, characterized in that it comprises a microwave reactor (1), an air reactor (13), a oxyfuel reactor (3) and an oxyfuel-lean reactor (8); the microwave reactor (1) is communicated with the oxyfuel reactor (3) through a desulfurization fuel conveying pipeline (2); the bottom of the oxyfuel reactor (3) is communicated with the oxygen-deficient fuel reactor (8) through a fuel reactor connecting pipeline (5), and a regulating valve (7) is arranged on the fuel reactor connecting pipeline (5) and is used for regulating the peroxy coefficient R in the oxygen-deficient fuel reactor (8); the bottom of the oxyfuel reactor (3) is provided with a fluidization medium inlet D; the bottom of the oxyfuel reactor (3) is communicated with an air reactor (13) through a first feed back pipe (6); the bottom of the oxygen-deficient fuel reactor (8) is communicated with an air reactor (13) through a second feed back pipe (12); the bottom of the oxygen-deficient fuel reactor (8) is provided with a mixed fluidization medium inlet F; the mixed fluidization medium inlet F is provided with a first flue gas analyzer (10) for monitoring the inlet gas concentration of the oxygen-deficient fuel reactor (8), the air reactor (13) is communicated with the AR cyclone separator (22) through an air reactor riser (19), and the AR cyclone separator (22) is communicated with the oxygen-rich fuel reactor (3) through an AR cyclone separator dipleg (21).
7. The device for the chemical looping combustion directional desulfurization process coupled with microwave technology according to claim 6, wherein air distribution plates are arranged at the lower parts of the air reactor (13), the oxyfuel reactor (3) and the oxygen-deficient fuel reactor (8).
8. The device for the chemical looping combustion directional desulfurization process coupled to microwave technology according to claim 6, characterized in that a first cyclone separator (18) is installed on the upper portion of the oxy-fuel reactor (3), and high-purity CO is provided on the first cyclone separator (18) 2 Outlet E of the high purity CO 2 A third flue gas analyzer (20) is arranged at the outlet E and used for monitoring the concentration of sulfur-containing gas at the outlet of the oxy-foot reactor (3), and the first cyclone separator (18) is communicated with the oxy-foot fuel reactor (3) through a first cyclone separator dipleg (17) and used for returning part of unreacted solid fuel and oxygen carrier to the oxy-foot fuel reactor (3);
the upper part of the oxygen-deficient fuel reactor (8) is provided with a second cyclone separator (15), the second cyclone separator (15) is provided with a high-temperature fluidization medium outlet H, a second flue gas analyzer (16) is arranged at the high-temperature fluidization medium outlet H and is used for monitoring the concentration of sulfur-containing gas at the outlet of the oxygen-deficient fuel reactor (8), and the second cyclone separator (15) is communicated with the oxygen-deficient fuel reactor (8) through a second cyclone separator dipleg (14) and is used for returning separated solid particles to the oxygen-deficient fuel reactor (3).
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