CN110589760A - Chemical chain gasification reforming device and method for controllably removing and adding alkali metal or alkaline earth metal - Google Patents

Chemical chain gasification reforming device and method for controllably removing and adding alkali metal or alkaline earth metal Download PDF

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CN110589760A
CN110589760A CN201910796289.5A CN201910796289A CN110589760A CN 110589760 A CN110589760 A CN 110589760A CN 201910796289 A CN201910796289 A CN 201910796289A CN 110589760 A CN110589760 A CN 110589760A
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chemical
gasification reforming
alkaline earth
biomass
removal
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CN110589760B (en
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胡志锋
蒋恩臣
王明峰
任永志
吴家威
张键鑫
杨锋
林宗杰
黄祥能
苗桢武
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South China Agricultural University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • General Health & Medical Sciences (AREA)
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Abstract

The invention discloses a chemical chain gasification reforming device and a chemical chain gasification reforming method for controllably removing and adding alkali metal or alkaline earth metal, wherein the device comprises a removing component, an adding component, a spiral feeder, a chemical chain gasification reforming device, a cyclone separator and a gas purification device which are sequentially connected, and also comprises a liquid purification device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purification device is connected with the chemical chain gasification reforming device and provides water vapor for the chemical chain gasification reforming device; the method comprises the steps of stirring and pickling biomass raw materials with an acid solution in a magnetic stirring removal device, entering a magnetic stirring adding device after filter pressing and leaching, stirring and dipping with an alkali metal or alkaline earth metal solution, continuously stirring, uniformly mixing and reacting with an oxygen carrier and water vapor in a chemical chain gasification reforming device after filter pressing, adjusting the adding amount of the water vapor to controllably adjust the proportion of synthesis gas, continuously reacting the oxygen carrier in an air reactor, mixing with pretreated biomass again, and continuing the next cycle.

Description

Chemical chain gasification reforming device and method for controllably removing and adding alkali metal or alkaline earth metal
Technical Field
The invention relates to the technical field of chemical-looping gasification reforming, in particular to a chemical-looping gasification reforming device and a chemical-looping gasification reforming method capable of removing and adding alkali metal or alkaline earth metal controllably.
Background
Chemical looping gasification is a novel gasification technology. Chemical looping gasification systems typically consist of two reactors in series (a fuel reactor and an air reactor) with an oxygen carrier circulating between the two reactors. The lattice oxygen in the oxygen carrier serves as a medium for conventional gasification reactions throughout the cycle and provides the necessary oxygen element for the fuel gasification reaction. Furthermore, by controlling the ratio of lattice oxygen to fuel, H can be obtained2And syngas with CO as the main constituent. The technology has the advantages that oxygen carriers are used for circularly supplying oxygen, so that the cost is saved; can control H2And the proportion of CO, so that the ideal synthesis gas required by chemical products can be obtained conveniently; the oxygen carrier can catalyze and promote the reaction and improve the gasification reaction efficiency. Therefore, the exploration and development of the biomass chemical-looping gasification technology have extremely high application value.
The agricultural and forestry wastes have various types and large performance difference, and the types and the content of alkali metals in the biomass also have large difference. In the biomass gasification process, alkali metal and alkaline earth metal (AAEM) are used as trace elements with the largest content in agricultural and forestry waste, so that the problems of furnace hearth material slagging, heating surface ash deposition corrosion and the like are easily caused, and the combustion, pyrolysis and gasification reaction of biomass are hindered. Meanwhile, researches show that alkali metal or alkaline earth metal plays a certain role in catalysis or inhibition in the biomass pyrolysis, gasification and combustion processes, and the reaction process is uncontrolled, so that the differences of the reaction performance, the dynamic characteristic, the gas product precipitation characteristic and other performances of the biomass are obvious, and the efficiency and the safety of biomass centralized treatment are further influenced; in the gasification reaction, the gasification efficiency greatly fluctuates, and the gas quality is unstable, thereby affecting the quality of chemical products or the combustion condition.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a device for preparing synthesis gas by biomass chemical-looping gasification reforming, wherein alkali metals or alkaline-earth metals are removed and added controllably, the device can efficiently and continuously remove the alkali metals or the alkaline-earth metals of a biomass raw material, slow down the inhibition effect of the alkali metals or the alkaline-earth metals, and can controllably add the needed alkali metals or the alkaline-earth metals with the catalytic action, thereby achieving the purpose of efficiently pretreating the raw material of the chemical-looping gasification reaction.
Another object of the present invention is to provide a method for preparing synthesis gas by chemical looping gasification reforming of biomass, in which alkali metals or alkaline earth metals can be controllably removed and added, the method can combine raw material pretreatment and chemical looping gasification reforming reaction, reduce agglomeration of biomass and oxygen carriers during the reaction process, improve the reaction efficiency, and controllably adjust the composition of combustible gas during the reaction process.
The technical scheme of the invention is as follows: a chemical chain gasification reforming device for controllably removing and adding alkali metal or alkaline earth metal comprises a removing component, an adding component, a spiral feeder, a chemical chain gasification reforming device, a cyclone separator and a gas purification device which are sequentially connected, and further comprises a liquid purification device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purification device is connected with the chemical chain gasification reforming device and provides water vapor for the chemical chain gasification reforming device;
get rid of the subassembly including the magnetic stirring remove device who connects gradually, get rid of coil formula pressure filter and get rid of chain conveyor, add the subassembly including the magnetic stirring who connects gradually add the device, add coil formula pressure filter and add chain conveyor.
The liquid phase channel of the removal coil type filter press is connected with the liquid purification device, the solid phase channel of the removal coil type filter press is connected with the removal chain type conveyer belt, a leaching device is arranged above the removal chain type conveyer belt, and leaching water is introduced into the liquid purification device.
The liquid phase channel of the adding coil type filter press is connected with the liquid purification device, the solid phase channel of the adding coil type filter press is connected with the adding chain type conveyer belt, and the outlet end of the removing chain type conveyer belt is connected with the magnetic stirring adding device.
The spiral feeder adopts a shaftless spiral reactor, the inlet of the spiral feeder is connected with the outlet end of the adding chain type conveying belt, and the outlet of the spiral feeder is connected with the chemical chain gasification reforming device.
The chemical chain gasification reforming device adopts a shaftless spiral reactor, and comprises a feed inlet, a steam channel, an oxygen carrier circulation channel and a discharge port, wherein the feed inlet is connected with a spiral feeder, the steam channel is connected with a liquid purification device, a peristaltic pump is arranged between the steam channel and the liquid purification device, the discharge port is connected with a cyclone separator, a gas outlet of the cyclone separator is connected with a gas purification device and a gas storage tank, a solid outlet of the cyclone separator is connected with an air reactor, and the air reactor leads to the chemical chain gasification reforming device to form the oxygen carrier circulation channel.
A chemical looping gasification reforming process with controlled removal and addition of alkali or alkaline earth metals, the process comprising:
feeding the biomass raw material into a magnetic stirring removal device, adding an acid solution, continuously stirring in the magnetic stirring removal device for acid washing, separating water into a liquid purification device through a liquid phase channel by a removal rotary tube type filter press for purification treatment, and feeding the filter-pressed biomass into a removal chain conveyor belt through a solid phase channel;
during the process of removing chain conveyor belt and transporting biomass, continuously washing an acid solution on the biomass by a leaching device, conveying the washed biomass to a magnetic stirring adding device, simultaneously adding an alkali metal or alkaline earth metal solution into the magnetic stirring adding device, continuously stirring and dipping in the magnetic stirring adding device, separating water into a liquid purifying device through an adding coil type filter press through a liquid phase channel for purifying treatment, and conveying the filter-pressed biomass to a spiral feeder through a solid phase channel by an adding chain conveyor belt;
the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to the chemical-looping gasification reforming device and are uniformly mixed, and the biomass, the water vapor and the oxygen carrier react in the chemical-looping gasification reforming device;
products obtained by reaction in the chemical chain gasification reforming device are separated by a cyclone separator, and synthetic gas is treated by a gas purification device and then is sent into a gas storage tank; the solid product enters an air reactor from a solid outlet of the cyclone separator, the reduced oxygen carrier reacts with air in the air reactor to form an oxidized oxygen carrier, and the oxidized oxygen carrier is sent into the chemical-looping gasification reforming device again to complete the primary circulation of preparing the synthesis gas by the chemical-looping gasification reforming of the biomass with the controllable removal and addition of alkali metal or alkaline earth metal; the above circulation is repeatedly operated, and biomass pretreatment of continuously and controllably removing and adding alkali metals or alkaline earth metals can be realized.
The biomass raw materials are stirred and pickled for 1-5 hours in a magnetic stirring removal device, the mass ratio of an acid solution to the biomass raw materials is 10: 1-90: 1, the acid solution is hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and the mass concentration of the acid solution is not more than 9%.
The mass concentration of the alkali metal or alkaline earth metal solution added into the magnetic stirring and adding device is not more than 24%, the alkali metal or alkaline earth metal solution adopts corresponding inorganic salt or organic salt solution, and one salt solution is added singly or a plurality of salt solutions are mixed and added.
The reaction time of the biomass, the steam and the oxygen carrier in the chemical chain gasification reforming device is 15-40 min, the ratio of hydrogen to carbon monoxide in the synthesis gas is adjusted by controlling the adding amount of the steam in the chemical chain gasification reforming device, and the adjustable range of the ratio of the hydrogen to the carbon monoxide is 0.5-6.0.
In the circulation process, when the hydrogen concentration value in the synthesis gas is reduced by 5%, 10% of oxygen carrier is required to be taken out from the solid outlet of the cyclone separator for activation, and 10% of fresh oxygen carrier is required to be fed into the chemical chain gasification reforming device.
Compared with the prior art, the invention has the following beneficial effects:
1. the biomass is pickled by magnetic stirring, so that alkali metals or alkaline earth metals of the biomass raw material are efficiently removed, the inhibition effect of the biomass raw material on chemical chain gasification reforming reaction is slowed down, and the agglomeration and caking phenomena of the biomass and an oxygen carrier are reduced.
2. The method can controllably add the needed alkali metal or alkaline earth metal with catalytic action, improve the reaction efficiency of biomass chemical-looping gasification reforming, and control the adding amount of water vapor to controllably adjust the combustible gas components in the reaction process under the action of the alkali metal or alkaline earth metal.
3. The device has low price and strong practicability, the adopted method is simple and easy to implement, meets the environmental protection requirement, can be widely used in the agricultural and forestry waste thermochemical energy conversion processes such as biomass continuous pretreatment, continuous gasification reforming, rural distributed energy and the like, and has wide application prospect.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
FIG. 2 is a process flow diagram of the method of the present invention.
FIG. 3 shows the test results of example 2.
The reference numbers and corresponding part names in the figures are: the device comprises a magnetic stirring removal device 1, a removal coil type press filter 2, a leaching device 3, a liquid purification device 4, a chain conveyor belt 5, a magnetic stirring adding device 6, an addition coil type press filter 7, an addition chain conveyor belt 8, a peristaltic pump 9, a spiral feeder 10, a chemical chain gasification reforming device 11, a cyclone separator 12, an air reactor 13, a gas purification device 14 and a gas storage tank 15.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The chemical looping gasification reforming device for controllably removing and adding the alkali metal or the alkaline earth metal comprises a removing component for removing the AAEM, an adding component for adding the AAEM with catalytic action, a screw feeder, a chemical looping gasification reforming device for providing a reaction site, a cyclone separator and a gas purifying device which are sequentially connected, and further comprises a liquid purifying device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purifying device is connected with the chemical looping gasification reforming device and provides water vapor for the chemical looping gasification reforming device;
get rid of the subassembly including the magnetic stirring remove device who connects gradually, get rid of coil formula pressure filter and get rid of chain conveyor, add the subassembly including the magnetic stirring who connects gradually add the device, add coil formula pressure filter and add chain conveyor.
Get rid of the exit linkage of the entry of coil filter press and magnetic stirring remove device, the export of getting rid of coil filter press divides into two the tunnel, link to each other with liquid purification device for getting rid of the liquid phase passageway of coil filter press all the way, another way links to each other with the entry of getting rid of chain conveyor for getting rid of the solid phase passageway of coil filter press, it still is equipped with the drip washing device to get rid of chain conveyor top, the spray shower nozzle that chain conveyor set up is got rid of for a plurality of orientations to the drip washing device, the drip washing device is used for wasing remaining acid solution on the living beings, the drip washing water lets in liquid purification device and carries out waste water purification. The removal chain conveyor belt is controlled by a motor to control the conveying speed, and the speed of the motor is determined by the speed of the motor in the chemical chain gasification reforming device.
The inlet of the adding coil type filter press is connected with the outlet of the magnetic stirring adding device, the outlet of the adding coil type filter press is divided into two paths, one path is a liquid phase channel for adding the coil type filter press and is connected with a liquid purification device, the liquid purification device is used for purifying waste water, the other path is a solid phase channel for adding the coil type filter press and is connected with the inlet of the adding chain type conveying belt, and the outlet end of the removing chain type conveying belt is connected with the magnetic stirring adding device. The adding chain conveyer belt is controlled by a motor to control the conveying speed, and the speed of the motor is consistent with that of the motor for removing the chain conveyer belt.
The inlet of the screw feeder is connected with the outlet end of the adding chain type conveyer belt, the screw feeder adopts a shaftless screw reactor, and the outlet of the screw feeder is connected with the feed inlet of the chemical chain gasification reforming device. The feed rate is controlled by a motor whose speed is determined by the supply of material in the chemical looping gasification reformer.
The chemical chain gasification reforming device adopts a shaftless spiral reactor, the chemical chain gasification reforming device comprises a feed inlet, a steam channel, an oxygen carrier circulation channel and a discharge port, the feed inlet is connected with an outlet of a spiral feeder, the steam channel is connected with a liquid purification device, a peristaltic pump is arranged between the steam channel and the liquid purification device, the waste water treated by the liquid purification device provides steam required by reaction for the chemical chain gasification reforming device, the discharge port of the chemical chain gasification reforming device is connected with a cyclone separator, a reaction product is sent into the cyclone separator to separate solid particles in air flow by using centrifugal force, the cyclone separator is provided with a gas outlet and a solid outlet, the gas outlet of the cyclone separator is connected with a gas purification device and a gas storage tank, the solid outlet of the cyclone separator is connected with an air reactor, and the air reactor leads to the chemical chain gasification reforming device to form the oxygen carrier circulation channel, the air reactor is used for enabling the oxygen carrier to react with air, and then the oxygen carrier is sent into the chemical chain gasification reforming device to react with the water vapor and the biomass raw material, so that the cyclic utilization of the oxygen carrier is realized. The speed of the chemical-looping gasification reforming device is controlled by a motor, the speed of the motor is determined by the supply amount of materials, and meanwhile, the reaction time of the materials in the chemical-looping gasification reforming device is required to be guaranteed to reach 15-40 min. The rate at which the oxygen carrier is delivered by the air reactor outlet is determined by the ratio of the feed to the oxygen carrier feed.
The liquid purification device can adopt a purification device with multi-layer filtering and adsorption functions, and can adopt a conventional purification device on the market. The air reactor mainly adopts a circulating fluidized bed or a fixed bed, air is introduced, and the air reacts with the reduced oxygen carrier under the action of high temperature to form the oxygen carrier in an oxidation state. The gas purification device is mainly used for removing water vapor and tar in gas through condensation, and then removing tiny particles in the gas through cloth bag dust removal. The air reactor and the gas purification device can be conventional devices on the market, and are not described in detail herein.
The present embodiment also provides a chemical looping gasification reforming method with controllable removal and addition of alkali metals or alkaline earth metals, and fig. 2 is a flow chart of the method, which comprises the following steps:
the method comprises the steps of feeding the biomass raw material into a magnetic stirring removal device, adding an acid solution with the mass concentration not more than 9%, wherein the mass ratio of the acid solution to the biomass raw material is 10: 1-90: 1, and continuously stirring the acid solution in the magnetic stirring removal device by using hydrochloric acid, sulfuric acid, nitric acid or acetic acid for pickling for 1-5 hours. After acid washing is finished, the biomass enters a removal coil type filter press from an outlet of a magnetic stirring removal device, water is separated to a liquid purification device through a liquid phase channel by the removal coil type filter press for purification treatment, and the filter-pressed biomass enters a removal chain type conveyor belt through a solid phase channel;
during getting rid of chain conveyor belt transportation living beings, the acid solution on the living beings is washd in succession to the drip washing device, and liquid after the drip washing is carried to liquid purifier and is carried out waste water purification treatment, and the living beings after the washing are carried to magnetic stirring and are added the device, add alkali metal or alkaline earth metal solution that the mass concentration is no more than 24% in adding the device to magnetic stirring simultaneously, and the proportion scope of alkali metal or alkaline earth metal solution and living beings raw materials volume is 10:1 to 100: the alkali metal or alkaline earth metal solution adopts corresponding inorganic salt or organic salt solution, and one salt solution can be singly added or a plurality of salt solutions can be mixed and added. Continuously stirring and dipping in a magnetic stirring adding device for 1-5 h, separating water into a liquid purifying device through an adding coil type filter press through a liquid phase channel for purifying, and conveying the filter-pressed biomass to a screw feeder through an adding chain type conveying belt through a solid phase channel;
the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to a chemical-looping gasification reforming device, the shaftless spiral reactor is driven to continuously stir by regulating and controlling the rotating speed of a motor, so that the materials are uniformly mixed, and the biomass, the water vapor and the oxygen carrier in the chemical-looping gasification reforming device react for 15-40 min; the ratio of hydrogen to carbon monoxide in the synthesis gas is adjusted by controlling the adding amount of the steam in the chemical-looping gasification reforming device, and the adjustable range of the ratio of the hydrogen to the carbon monoxide is 0.5-6.0.
Products obtained by reaction in the chemical chain gasification reforming device are separated by a cyclone separator, and synthetic gas enters a gas purification device from a gas outlet of the cyclone separator for treatment and then is sent into a gas storage tank; solid products enter the air reactor from a solid outlet of the cyclone separator, reduced oxygen carriers react with air in the air reactor to form oxidized oxygen carriers, and the oxygen carriers are sent to the chemical-looping gasification reforming device again to circulate the oxygen carriers, so that primary circulation of preparing synthesis gas by biomass chemical-looping gasification reforming with controllable removal of alkali metals or alkaline-earth metals and addition is completed;
the above circulation is repeatedly operated, and biomass pretreatment of continuously and controllably removing and adding alkali metals or alkaline earth metals can be realized. Meanwhile, by detecting the concentration value of hydrogen in the gas phase product, if the concentration value of hydrogen in the synthesis gas is reduced by 5%, 10% of oxygen carriers need to be taken out from a solid outlet of the cyclone separator for activation, and 10% of fresh oxygen carriers need to be fed into the chemical-looping gasification reforming device.
Example 2
In this example, the apparatus of example 1 was used to test the changes in the effect of the concentration of synthesis gas and the reaction efficiency of the invention using rice hulls having a water content of 8.47% as biomass feedstock. In which 3 control groups were set: one is a control group 1 and is a blank control group, and the rice hulls directly carry out chemical chain gasification reforming reaction without removing and adding alkali metal or alkaline earth metal; one is a control group 2, the rice hulls are subjected to chemical chain gasification reforming reaction after alkali metal or alkaline earth metal is removed but no alkali metal or alkaline earth metal is added; the other is a control group 3, the rice hulls are removed and added with alkali metal or alkaline earth metal, and then chemical chain gasification reforming reaction is carried out. The effect achieved by the present invention is demonstrated by comparing the syngas concentrations and reaction efficiencies produced by these 3 controls.
The specific operation steps of the control group 3 are as follows:
(1) sending the rice hulls with the water content of 8.47% into a magnetic stirring removal device, adding a nitric acid solution with the mass concentration of 5% at the same time, wherein the mass ratio of the nitric acid solution to the biomass raw material is 50: 1, continuously stirring in a magnetic stirring removal device to carry out acid washing for 3 hours, after the acid washing is finished, feeding the mixture into a removal coil type press filter from an outlet of the magnetic stirring removal device, separating water into a liquid purification device through a liquid phase channel by the removal coil type press filter to carry out purification treatment, and feeding the filter-pressed biomass into a removal chain conveyor belt through a solid phase channel;
(2) during getting rid of chain conveyor belt transportation living beings, the acid solution on the living beings is washd in succession to the drip washing device, and liquid after the drip washing is carried to liquid purifier and is carried out waste water purification treatment, and the living beings after the washing are carried to magnetic stirring and are added the device, add the calcium acetate solution that the mass concentration is 3% in adding the device toward magnetic stirring simultaneously, and calcium acetate solution and rice husk volume proportion are 100: 1, continuously stirring and dipping for 3 hours in a magnetic stirring and adding device, separating water to a liquid purification device through a liquid phase channel by an adding coil type filter press for purification treatment, and conveying the filter-pressed biomass to a spiral feeder through a solid phase channel by an adding chain type conveyer belt;
(3) the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to a chemical-looping gasification reforming device, the shaftless spiral reactor is driven to continuously stir by regulating and controlling the rotating speed of a motor, so that the materials are uniformly mixed, and the biomass, the water vapor and the oxygen carrier in the chemical-looping gasification reforming device react for 30 min; the reaction temperature of the chemical chain gasification reforming device is set to be 800 ℃, the oxygen carrier is prepared by a coprecipitation method of ferric nitrate and aluminum nitrate, the ratio of the oxygen carrier to the rice hulls is 1.5, and the flow of water introduced by a peristaltic pump per hour is 3 times of the amount of the rice hulls.
(4) Products obtained by reaction in the chemical-looping gasification reforming device are separated by a cyclone separator, synthetic gas enters a gas purification device from a gas outlet of the cyclone separator for treatment and then is sent into a gas storage tank, and then the gas is taken out from the gas storage tank for detection; and the solid product enters the air reactor from a solid outlet of the cyclone separator, the reduced oxygen carrier reacts with air in the air reactor to form an oxidized oxygen carrier, and the oxidized oxygen carrier is sent to the chemical-looping gasification reforming device again for circulation of the oxygen carrier, so that primary circulation of preparing the synthesis gas by the biomass chemical-looping gasification reforming with controllable removal and addition of alkali metal or alkaline earth metal is completed.
The above is the whole test process of the control group 3, the test process of the control group 1 does not pass through the steps (1) and (2), and directly passes through the steps (3) and (4), and the test process of the control group 2 does not pass through the step (1), and directly passes through the steps (2) to (4).
The test results are shown in fig. 3 and table 1. As can be seen from fig. 3, the hydrogen content of the control group 3 was slightly increased and the carbon dioxide concentration was decreased after the treatment according to the present invention, and the concentrations of carbon monoxide and methane were not significantly different from those of the control group 1. Showing that the effective components of the syngas are increased after the treatment of the present invention.
As can be seen from table 1, compared with the control group 1, after removing the alkali metal or alkaline earth metal in the rice hull, the carbon conversion efficiency and the gasification efficiency of the control group 2 are respectively improved by 20.92% and 29.44%; after the treatment of the present invention, the carbon conversion efficiency and gasification efficiency of the control group 3 were improved by 73.64% and 88.75%, respectively, compared to the control group 1. Therefore, after the alkali metal or the alkaline earth metal is controllably removed and added, the effective components of the synthesis gas subjected to chemical-looping gasification reforming are increased, and the carbon conversion efficiency and the gasification efficiency are greatly improved.
TABLE 1 comparison of carbon conversion efficiency and Oxidation efficiency for each control group
Control group Carbon conversion efficiency (%) Gasification efficiency (%)
1 24.66 43.04
2 29.82 55.71
3 42.82 81.24
As mentioned above, the present invention can be better realized, and the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; all equivalent changes and modifications made according to the present disclosure are intended to be covered by the scope of the claims of the present invention.

Claims (10)

1. The chemical-looping gasification reforming device capable of controllably removing and adding the alkali metal or the alkaline earth metal is characterized by comprising a removing component, an adding component, a spiral feeder, a chemical-looping gasification reforming device, a cyclone separator and a gas purifying device which are sequentially connected, and further comprising a liquid purifying device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purifying device is connected with the chemical-looping gasification reforming device and provides water vapor for the chemical-looping gasification reforming device;
get rid of the subassembly including the magnetic stirring remove device who connects gradually, get rid of coil formula pressure filter and get rid of chain conveyor, add the subassembly including the magnetic stirring who connects gradually add the device, add coil formula pressure filter and add chain conveyor.
2. The chemical looping gasification reforming device for removing and adding alkali metals or alkaline earth metals controllably as claimed in claim 1, wherein the liquid phase channel of the removal coil type filter press is connected with a liquid purification device, the solid phase channel of the removal coil type filter press is connected with a removal looping conveyor belt, a leaching device is arranged above the removal looping conveyor belt, and leaching water is introduced into the liquid purification device.
3. The chemical looping gasification reforming device for the controlled removal and addition of alkali metals or alkaline earth metals as claimed in claim 1, wherein the liquid phase channel of the additional spiral tube type pressure filter is connected with a liquid purification device, the solid phase channel of the additional spiral tube type pressure filter is connected with an additional looping conveyor belt, and the outlet end of the removal looping conveyor belt is connected with a magnetic stirring and adding device.
4. The chemical looping gasification reforming device for removing and adding alkali metals or alkaline earth metals in a controlled manner as claimed in claim 1, wherein the screw feeder is a shaftless screw reactor, an inlet of the screw feeder is connected with an outlet end of the adding chain conveyor belt, and an outlet of the screw feeder is connected with the chemical looping gasification reforming device.
5. The chemical looping gasification reforming device for removing and adding the alkali metal or the alkaline earth metal controllably according to claim 1, characterized in that the chemical looping gasification reforming device adopts a shaftless spiral reactor, the chemical looping gasification reforming device comprises a feed inlet, a water vapor channel, an oxygen carrier circulation channel and a discharge outlet, the feed inlet is connected with a spiral feeder, the water vapor channel is connected with a liquid purification device, a peristaltic pump is arranged between the water vapor channel and the liquid purification device, the discharge outlet is connected with a cyclone separator, a gas outlet of the cyclone separator is connected with the gas purification device and a gas storage tank, a solid outlet of the cyclone separator is connected with an air reactor, and the air reactor leads to the chemical looping gasification reforming device to form the oxygen carrier circulation channel.
6. A chemical looping gasification reforming process with controlled removal and addition of alkali or alkaline earth metals, the process comprising:
feeding the biomass raw material into a magnetic stirring removal device, adding an acid solution, continuously stirring in the magnetic stirring removal device for acid washing, separating water into a liquid purification device through a liquid phase channel by a removal rotary tube type filter press for purification treatment, and feeding the filter-pressed biomass into a removal chain conveyor belt through a solid phase channel;
during the process of removing chain conveyor belt and transporting biomass, continuously washing an acid solution on the biomass by a leaching device, conveying the washed biomass to a magnetic stirring adding device, simultaneously adding an alkali metal or alkaline earth metal solution into the magnetic stirring adding device, continuously stirring and dipping in the magnetic stirring adding device, separating water into a liquid purifying device through an adding coil type filter press through a liquid phase channel for purifying treatment, and conveying the filter-pressed biomass to a spiral feeder through a solid phase channel by an adding chain conveyor belt;
the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to the chemical-looping gasification reforming device and are uniformly mixed, and the biomass, the water vapor and the oxygen carrier react in the chemical-looping gasification reforming device;
products obtained by reaction in the chemical chain gasification reforming device are separated by a cyclone separator, and synthetic gas is treated by a gas purification device and then is sent into a gas storage tank; the solid product enters an air reactor from a solid outlet of the cyclone separator, the reduced oxygen carrier reacts with air in the air reactor to form an oxidized oxygen carrier, and the oxidized oxygen carrier is sent into the chemical-looping gasification reforming device again to complete the primary circulation of preparing the synthesis gas by the chemical-looping gasification reforming of the biomass with the controllable removal and addition of alkali metal or alkaline earth metal; the above circulation is repeatedly operated, and biomass pretreatment of continuously and controllably removing and adding alkali metals or alkaline earth metals can be realized.
7. The chemical looping gasification reforming method for controllably removing and adding alkali metals or alkaline earth metals as claimed in claim 6, wherein the biomass raw material is stirred and pickled for 1-5 hours in a magnetic stirring removal device, the mass ratio of the acid solution to the biomass raw material is 10: 1-90: 1, the acid solution is hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and the mass concentration of the acid solution is not more than 9%.
8. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals controllably according to claim 6, characterized in that the mass concentration of the alkali metal or alkaline earth metal solution added in the magnetic stirring adding device is not more than 24%, the alkali metal or alkaline earth metal solution adopts corresponding inorganic salt or organic salt solution, and one salt solution is added singly or a plurality of salt solutions are added in a mixing way.
9. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals in a controllable manner according to claim 6, wherein the reaction time of the biomass, the steam and the oxygen carrier in the chemical looping gasification reforming device is 15-40 min, the ratio of hydrogen to carbon monoxide in the synthesis gas is adjusted by controlling the adding amount of the steam in the chemical looping gasification reforming device, and the ratio of the hydrogen to the carbon monoxide can be adjusted within the range of 0.5-6.0.
10. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals controllably according to claim 9, characterized in that, in the circulation process, when the hydrogen concentration value in the synthesis gas is reduced by 5%, 10% of oxygen carriers are required to be taken out from the solid outlet of the cyclone for activation, and 10% of fresh oxygen carriers are required to be fed into the chemical looping gasification reforming device.
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