CN112322362A - Method and device for negative utilization of biomass carbon by using molten salt - Google Patents

Method and device for negative utilization of biomass carbon by using molten salt Download PDF

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CN112322362A
CN112322362A CN202011138093.6A CN202011138093A CN112322362A CN 112322362 A CN112322362 A CN 112322362A CN 202011138093 A CN202011138093 A CN 202011138093A CN 112322362 A CN112322362 A CN 112322362A
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absorbent
regeneration
reactor
molten salt
biomass
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CN112322362B (en
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王小波
赵增立
郑安庆
刘安琪
蒋丽群
李海滨
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Guangzhou Institute of Energy Conversion of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • 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
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/122—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/22—Apparatus, e.g. dry box purifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/30—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses with moving purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

The invention discloses a method and a device for utilizing carbon negativity of biomass by using molten salt. The method comprises the following steps: (1) the biomass enters a downdraft fixed bed gasification furnace to be gasified, and combustible gas containing tar and gasified solid products are generated under the action of a gasification agent; (2) three-phase reforming: the combustible gas containing tar enters three-phase reforming reactionReforming in a reactor, wherein the reforming reactor is filled with a mixed absorbent, and the temperature of the reforming reaction is 400-700 ℃; (3) regeneration of an absorbent: the mixed absorbent after the reforming reaction enters an absorbent regeneration reactor for regeneration, the mixed absorbent is recovered to the state before use after regeneration, and CO is released2. The invention combines the gasification process of carbon neutral fuel biomass with the technical items of carbon capture and carbon sequestration, reduces the carbon negative utilization of the biomass by reducing the carbon discharged to the atmosphere in the conversion process of the biomass energy, and provides a method for reducing CO in the atmosphere while meeting the energy requirement2The pathway of (1).

Description

Method and device for negative utilization of biomass carbon by using molten salt
Technical Field
The invention relates to the technical field of biomass energy utilization, in particular to a method and a device for utilizing carbon negativity of biomass by utilizing molten salt.
Background
Biomass is a large and ubiquitous source of renewable energy. Biomass is a low carbon energy source with lower sulfur and ash content and higher oxygen content than coal. Since biomass is a carbon neutral fuel, it is possible to achieve negative carbon utilization of biomass by reducing the carbon emitted to the atmosphere during conversion of biomass energy. This process is performed by combining Biomass Energy utilization (BE) with Carbon Capture and Storage (CCS) (i.e., BECCS, Biomass with carbon capture and storage). The BECCS process provides a means of reducing atmospheric CO while meeting energy requirements2The pathway of (1).
Patent CN106675655A discloses a biomass chemical-looping gasification hydrogen production device and method based on calcium-based carbon carriers, which comprises a biomass gasification furnace, a calcium-based carbon carrier calcining furnace, a cyclone separator, an upper material return valve and a lower material return valve; when in use, the temperature to be operated reaches the pre-operation temperatureWhen the working temperature is set, and the working pressure of the two furnace bodies is micro-positive pressure, adding the calcium-based carbon carrier from a calcium-based carbon carrier spiral feed inlet of the calcium-based carbon carrier calcining furnace, adding biomass particles into a biomass spiral feed inlet, adjusting the ratio of steam to biomass and the solid fluidization speed according to the on-site requirement, and opening a water circulation valve of a waste heat recovery chamber after the solid fluidization speed is kept stable; the carbon carrying capacity of the calcium-based carbon carrier is reduced along with the increase of the circulation times of the calcium-based carbon carrier, and CO measured at the flue gas outlet of the cyclone separator and the flue gas outlet of the gasification furnace at the moment2Adjusting the feeding speed of fresh calcium-based carbon carrier in the calciner, opening a large particle channel of the calciner at the same time, and discharging the sintered and agglomerated large particle substances into a slag hole of a lower air chamber for discharging. The patent adopts the traditional solid calcium-based absorbent as bed material and CO2The absorbent absorbs CO generated in the biomass gasification process2. The reaction process is a solid-solid reaction and a gas-solid reaction process, and the mass transfer efficiency of the reaction process is poor. In the absorption process, the absorbent is directly contacted with the biomass raw material, and the absorbent is easily inactivated due to ash and harmful impurities in the raw material. Patent CN109913272A discloses a device and a process for preparing hydrogen-rich synthesis gas by absorbing and strengthening biomass gasification in molten salt, wherein the process comprises the following steps: biomass particles and water vapor are introduced into a reactor containing molten salt together, the biomass is pyrolyzed in the molten salt to obtain primary fuel gas, tar and coke which is not completely reacted, the coke and the water vapor react in the molten salt to generate primary synthetic gas, volatile components (the primary fuel gas, the tar and the primary synthetic gas) generated by the reaction and excessive water vapor enter an absorbent particle bed layer in an absorption chamber to carry out reforming reaction, and products after the reforming reaction are condensed to remove the water vapor, so that a hydrogen-rich synthetic gas product is obtained. The biomass adopted by the method is wood chips, straws, corncobs, shells, straws and the like; the adopted molten salt is a eutectic of lithium carbonate, sodium carbonate and potassium carbonate, and the mass ratio of the lithium carbonate to the sodium carbonate to the potassium carbonate is 30-34: 31-35: 32-38; the absorbent particles are spherical calcium oxide, dolomite, olivine, etc. The adopted molten salt is inert carbonate, and the molten salt does not participate in absorption reaction in the reaction process. And the process needs to introduce excessive water vapor to realize high conversion absorptivity of the carbon-containing combustible gas, and meanwhile, even if excessive water vapor is introduced, the complete conversion of the carbon-containing combustible gas is difficult to realize.
None of the above patents relates to the utilization of a molten salt and calcium-based mixed absorbent having reaction characteristics to achieve negative heat utilization of biomass carbon.
Disclosure of Invention
The invention provides a method and a device for utilizing molten salt to carry out negative carbon utilization of biomass, which are simple and convenient to operate and strong in process adaptability2The pathway of (1).
The invention aims to provide a method for negative utilization of biomass carbon by using molten salt, which comprises the following steps:
(1) biomass gasification: the biomass enters a downdraft fixed bed gasification furnace to be gasified, and combustible gas containing tar and gasified solid products are generated under the action of a gasification agent;
(2) three-phase reforming: the combustible gas containing tar in the step (1) enters a three-phase reforming reactor for reforming, the reforming reactor is filled with a mixed absorbent, the temperature of the reforming reaction is 400-700 ℃, the mixed absorbent comprises liquid molten salt and solid calcium-based particles, and the solid calcium-based particles are CaO and/or Ca (OH)2The molten salt comprises MOH and M2CO3Wherein M is an alkali metal, n (MOH): n (M)2CO3)10-30: 70-90, wherein the molar ratio of the molten salt to calcium in the solid calcium-based particles is n (MOH + M)2CO3):n(Ca)＝5:1～1:1；
(3) Regeneration of an absorbent: the mixed absorbent after the reforming reaction in the step (2) enters an absorbent regeneration reactor for regeneration, and is mixed and absorbedThe agent is regenerated and then restored to the state before use, and CO is released2The regeneration temperature is 1000-1200 ℃. The molten salt regeneration heat source can be derived from high-temperature gas, electric heat and the like. The tar-containing combustible gas mainly contains CO and CO2、H2、 CH4Tar and small amounts of gaseous hydrocarbons.
The method comprises the main steps of biomass gasification, three-phase reforming, absorbent regeneration and the like. The biomass raw material subjected to primary pretreatment is gasified in a downdraft fixed bed gasifier, and combustible gas containing tar enters a three-phase reforming reactor to be reformed to obtain CH4And H2The mixed absorbent used by the three-phase reforming reactor is regenerated at high temperature in the absorbent regeneration reactor to obtain CO as the by-product2。
Preferably, in the step (2), the solid calcium-based particles and the liquid molten salt are in a fluidized state under the action of combustible gas containing tar, and the combustible gas containing tar becomes mixed gas mainly containing methane and hydrogen under the action of the liquid molten salt and the solid calcium-based particles.
Preferably, the gasification temperature in the step (1) is 700-900 ℃.
Preferably, the gasifying agent in the step (1) is one or more selected from air, water vapor, oxygen and carbon dioxide.
More preferably, the gasifying agent in the step (1) is one or more selected from the group consisting of steam, oxygen and carbon dioxide.
Preferably, the diameter of the solid calcium-based particles in the step (2) is between 0.01 and 1 mm.
Preferably, M in step (2) is selected from one of lithium, sodium and potassium.
The tar in the gasified gas (combustible gas containing tar) in the three-phase reforming reactor is at ultrahigh concentration of alkali metal ion M+、 OH-And catalytic cracking at high temperature.
Figure BDA0002737329180000041
CH removal in gasification gas production4The other carbonaceous components are adsorbed and fixed by reacting with MOH and CaO in the absorbent mixture.
CO2+MaOH→M2CO3+H2O (2)
Figure BDA0002737329180000042
Figure BDA0002737329180000043
In the absorbent mixture, CO2Preferentially react with more reactive MOH to form M2CO3Followed by melt mixing M in a liquid state2CO3With calcium-based absorbents (e.g. CaO, Ca (OH)2Etc.) reaction to form solid CaCO3。
Ultra-high concentration of alkali metal ions M in CO in gas+、OH-And carrying out water-gas shift reaction under the action of high temperature.
Figure BDA0002737329180000044
CO2Is absorbed and fixed to CaCO by the aforementioned process3In (1).
When melting and mixing the calcium-based absorbent (such as CaO, Ca (OH)) in the absorbent2Etc.) reaction (3) and/or (4) no longer occurs after the reaction is consumed, and the MOH in the absorbent mixture is gradually consumed by reaction (2). CH removal in the gasification gas production by the above reaction as shown in FIG. 44The other carbon-containing components are absorbed and fixed by reacting with MOH and CaO in the mixed absorbent, and the main components of the gasified gas production are converted into H2And CH4. The reformed gasified gas flows out of the three-phase reforming reactor from the first gas outlet to obtain the gas which does not contain CO and CO2The gasified fuel gas.
Absorption in a three-phase reforming reactorThe method comprises the steps that a mixed absorbent after carbon-containing gas saturation enters an absorbent regeneration reactor from an absorbent circulation outlet through a regeneration inlet, and the mixed absorbent is regenerated to release CO at 1000-1200 ℃ under the action of a heater in the absorbent regeneration reactor2. As shown in fig. 5, the mixed absorbent can be restored to an original state by high-temperature regeneration. Regeneration to release CO2And exits the absorbent regeneration reactor through a second gas outlet. Regenerating the obtained CO2The carbon dioxide gasification system can be used as a chemical raw material for producing epoxide, cyclohexene oxide and the like, and can also be sealed, and the external carbon dioxide emission of the whole gasification system is a negative value. The regenerated mixed absorbent is recycled back to the three-phase reforming reactor from the regeneration outlet through the absorbent recycling inlet.
The invention also protects a device for realizing the method for carrying out negative utilization of biomass carbon by using molten salt, which comprises a downdraft fixed bed gasification furnace, a three-phase reforming reactor and an absorbent regeneration reactor, wherein the top of the downdraft fixed bed gasification furnace is provided with a feed inlet which is connected with a feeding device, the lower part of the downdraft fixed bed gasification furnace is provided with a gasification agent air inlet, the bottom of the downdraft fixed bed gasification furnace is provided with a grate and an air outlet, the lower part of the grate is provided with an ash outlet, the air outlet is communicated with an air distribution plate at the bottom of the three-phase reforming reactor, the lower part of the three-phase reforming reactor is provided with an absorbent circulation inlet and an air outlet, the absorbent circulation outlet is communicated with a regeneration inlet of the absorbent regeneration reactor, the absorbent circulation inlet is connected with a regeneration outlet of the absorbent regeneration reactor, a heater is arranged in the absorbent regeneration reactor, and a gas outlet is arranged at the top of the absorbent regeneration reactor; biomass sequentially enters a downdraft fixed bed gasification furnace through a feeding device and a feeding hole, is gasified under the action of a gasification agent introduced from a gasification agent inlet to obtain a gasified solid product and combustible gas containing tar, the gasified solid product is separated from the combustible gas containing the tar through a grate, the gasified solid product is discharged through an ash outlet, the combustible gas containing the tar flows out of an air outlet and enters a three-phase reforming reactor through an air distribution plate to carry out reforming reaction, and the combustible gas after the reforming reactionGas flows out of the three-phase reforming reactor from the first gas outlet, the absorbent mixture after the reforming reaction enters the absorbent regeneration reactor from the absorbent circulation outlet through the regeneration inlet, and the absorbent mixture is regenerated at 1000-1200 ℃ to release CO under the action of a heater in the absorbent regeneration reactor2Regeneration of the liberated CO2Flows out of the regeneration reactor through the second gas outlet, and the regenerated absorbent mixture is recycled back to the three-phase reforming reactor from the regeneration outlet through the absorbent recycling inlet.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the mixture of the molten salt with reactivity and the calcium absorbent as the mixed absorbent, combines the gasification process of the carbon neutral fuel biomass with the technical items of carbon capture and carbon sequestration, reduces the carbon negative utilization of the biomass by reducing the carbon discharged to the atmosphere in the conversion process of the biomass energy, and provides the biomass energy-saving carbon-carbon composite absorbent which meets the energy requirement and reduces the CO in the atmosphere2The pathway of (1).
Drawings
FIG. 1 is a schematic diagram of an apparatus for negative utilization of biomass carbon by molten salt according to the present invention;
FIG. 2 is a diagram showing the operation state of materials in the device when the system is operated in the method for realizing the negative utilization of biomass carbon by using molten salt;
FIG. 3 is a material operation schematic diagram of the method for realizing negative utilization of biomass carbon by using molten salt;
FIG. 4 is a graph of gasification gas composition as a function of temperature after reforming absorption;
FIG. 5 shows molten salt and CaO mixed absorbent CO2The composition of the latter mixture;
description of reference numerals: 1. a downdraft fixed bed gasifier; 11. a feeding device; 12. a feed inlet; 13. an air inlet; 14. an air outlet; 15. a grate; 16. an ash outlet; 2. a three-phase reforming reactor; 21. a wind distribution plate; 22. an absorbent recycle outlet; 23. An absorbent circulation inlet; 24. a first gas outlet; 3. an absorbent regeneration reactor; 31. a regeneration inlet; 32. a regeneration outlet; 33. a second gas outlet; 34. a heater.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
As shown in fig. 1-5, a method for negative utilization of biomass carbon by molten salt comprises the following steps:
(1) biomass gasification: the biomass enters a downdraft fixed bed gasification furnace 1 for gasification, combustible gas containing tar and a gasified solid product are generated under the action of a gasification agent, the gasification temperature is 800 ℃, the gasification agent is a mixture of water vapor and oxygen, the proportion of the oxygen and the water vapor is adjusted by controlling the gasification temperature to be 800 ℃, and the gasification equivalence ratio is 0.28;
(2) three-phase reforming: the combustible gas containing tar in the step (1) enters a three-phase reforming reactor 2 for reforming, an absorbent mixture is filled in the reforming reactor, the temperature of the reforming reaction is 500 ℃, the absorbent mixture comprises liquid molten salt and solid calcium-based particles, the solid calcium-based particles are calcium oxide, the diameter of the calcium oxide particles is 0.1mm, and the main component of the molten salt is NaOH + Na2CO3Mixture of (3), NaOH and Na2CO3The molar ratio is NaOH: na (Na)2CO312.5: 87.5; molar ratio M (NaOH + Na) of molten salt mixture to calcium absorbent2CO3) M (Ca) is 5:1, calcium-based particles and liquid molten salt are in a fluidized state under the action of combustible gas, and the combustible gas becomes mixed gas mainly comprising methane and hydrogen under the action of the molten salt and the calcium-based particles;
(3) regeneration of an absorbent: the absorbent mixture after the reforming reaction in the step (2) enters an absorbent regeneration reactor 3 for regeneration, the absorbent mixture is recovered to the state before use after regeneration, and CO is released2The regeneration temperature is 1000 ℃, the absorbent mixture is recovered to the state before use after regeneration, and CO is released2. The source of the molten salt regeneration heat can be derived fromThe high-temperature gas generated by methane combustion has the flue gas temperature of about 1300 ℃.
The device for realizing the method for negatively utilizing the biomass carbon by using the molten salt comprises a downdraft fixed bed gasification furnace 1, a three-phase reforming reactor 2 and an absorbent regeneration reactor 3. The downdraft fixed bed gasification furnace 1 has a feed inlet 12 at the top, the feed inlet 12 is connected with a feed device 11, an air inlet 13 is arranged at the middle lower part, a grate 15 and an air outlet 14 are arranged at the bottom, and an ash outlet 16 is arranged below the grate 15. The air outlet 14 is communicated with an air distribution plate 21 at the bottom of the three-phase reforming reactor 2, the lower part of the three-phase reforming reactor 2 is provided with an absorbent circulating outlet 22, and the middle upper part is provided with an absorbent circulating inlet 23 and a first gas outlet 24. The absorbent circulation outlet 22 is connected to a regeneration inlet 31 of the absorbent regeneration reactor 3, and the absorbent circulation inlet 23 is connected to a regeneration outlet 32 of the absorbent regeneration reactor 3. The absorbent regeneration reactor 3 is internally provided with a heater 34, and the top of the absorbent regeneration reactor 3 is provided with a second gas outlet 33.
The biomass raw material after the preliminary pretreatment enters the downdraft fixed bed gasification furnace 1 through the feeding device 11 and the feeding hole 12, and is gasified under the action of the gasification agent fed in the gas inlet 13, the gasification temperature is 800 ℃, gasification ash and gasification gas are obtained, the gasification ash is separated from the gasification gas through the grate 15, and the gasification ash is discharged out of the downdraft fixed bed gasification furnace 1 through the ash outlet 16. The main components of gasification gas production are CO and CO2、H2、CH4Tar and small amounts of gaseous hydrocarbons: such as C2H4、C2H6And the gasification gas flows out of the downdraft fixed bed gasification furnace 1 from the gas outlet 14 and enters the three-phase reforming reactor 2 through the air distribution plate 21.
The tar in the gasified gas (combustible gas containing tar) in the three-phase reforming reactor is at ultrahigh concentration of alkali metal ion M+、 OH-And catalytic cracking at high temperature.
Figure BDA0002737329180000081
CH removal in gasification gas production4The other carbonaceous components are adsorbed and fixed by reacting with MOH and CaO in the absorbent mixture.
CO2+MaOH→M2CO3+H2O (2)
Figure BDA0002737329180000091
Figure BDA0002737329180000092
In the absorbent mixture, CO2Preferentially react with more reactive MOH to form M2CO3Followed by melt mixing M in a liquid state2CO3With calcium-based absorbents (e.g. CaO, Ca (OH)2Etc.) reaction to form solid CaCO3。
Ultra-high concentration of alkali metal ions M in CO in gas+、OH-And carrying out water-gas shift reaction under the action of high temperature.
Figure BDA0002737329180000093
CO2Is absorbed and fixed to CaCO by the aforementioned process3In (1).
When melting and mixing the calcium-based absorbent (such as CaO, Ca (OH)) in the absorbent2Etc.) reaction (3) and/or (4) no longer occurs after the reaction is consumed, and the MOH in the absorbent mixture is gradually consumed by reaction (2). CH removal in the gasification gas production by the above reaction as shown in FIG. 44The other carbon-containing components are absorbed and fixed by reacting with MOH and CaO in the mixed absorbent, and the main components of the gasified gas production are converted into H2And CH4. The reformed gasification gas flows out of the three-phase reforming reactor 2 from the first gas outlet 24 to obtain the gas without CO and CO2The gasified fuel gas. The gas composition at each position of the reaction system is shown in Table 1.
TABLE 1 gas composition (%) -at various locations of the system
Figure BDA0002737329180000094
The mixed absorbent saturated by the carbon-containing gas absorbed in the three-phase reforming reactor 2 enters the absorbent regeneration reactor 3 from the absorbent circulation outlet 22 through the regeneration inlet 31, and the mixed absorbent is regenerated at 1000 ℃ to release CO under the action of a heater 34 in the absorbent regeneration reactor 32. As shown in fig. 5, the mixed absorbent can be restored to the original state by high-temperature regeneration. Regeneration to release CO2Exits the absorbent regeneration reactor through a second gas outlet 33. Regenerating the obtained CO2The carbon dioxide gasification system can be used as a chemical raw material for producing epoxide, cyclohexene oxide and the like, and can also be sealed, and the emission of the carbon dioxide outside the whole gasification system is a negative value. The regenerated mixed absorbent is recirculated from the regeneration outlet back to the three-phase reforming reactor through the absorbent circulation inlet 23.
Example 2
Reference example 1 was made, with the difference that: the gasification temperature of the downdraft fixed bed gasification furnace is 900 ℃, the gasification agent is air, and the gasification equivalence ratio is 0.29; reforming temperature is 400 ℃, solid calcium-based particles are Ca (OH)2Particles, Ca (OH)2The particle diameter is 0.01mm, and the molten salt mainly comprises KOH + K2CO3The molten salt mainly comprises KOH + K2CO3The molar ratio of the mixture of (a) to (b) is KOH: k2CO330: 70; the regeneration temperature is 1200 ℃; the molten salt regeneration heat source is electric heat. The gas composition at each position of the reaction system is shown in Table 2.
TABLE 2 gas composition (%) -at various locations of the system
Figure BDA0002737329180000101
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (8)

1. A method for negative utilization of biomass carbon by using molten salt is characterized by comprising the following steps:
(1) biomass gasification: the biomass enters a downdraft fixed bed gasification furnace to be gasified, and combustible gas containing tar and gasified solid products are generated under the action of a gasification agent;
(2) three-phase reforming: the combustible gas containing tar in the step (1) enters a three-phase reforming reactor for reforming, the reforming reactor is filled with a mixed absorbent, the temperature of the reforming reaction is 400-700 ℃, the mixed absorbent comprises liquid molten salt and solid calcium-based particles, and the solid calcium-based particles are CaO and/or Ca (OH)2The molten salt comprises MOH and M2CO3Wherein M is an alkali metal, n (MOH): n (M)2CO3)10-30: 70-90, wherein the molar ratio of the molten salt to calcium in the solid calcium-based particles is n (MOH + M)2CO3):n(Ca)＝5:1～1:1；
(3) Regeneration of an absorbent: the mixed absorbent after the reforming reaction in the step (2) enters an absorbent regeneration reactor for regeneration, the mixed absorbent is recovered to the state before use after regeneration, and CO is released2The regeneration temperature is 1000-1200 ℃.
2. The method for negative utilization of biomass carbon using molten salt according to claim 1, wherein in the step (2), the solid calcium-based particles and the liquid molten salt are in a fluidized state by a tar-containing combustible gas, and the tar-containing combustible gas becomes a mixed gas mainly containing methane and hydrogen gas by the liquid molten salt and the solid calcium-based particles.
3. The method for negative utilization of biomass carbon using molten salt according to claim 1, wherein the gasification temperature in step (1) is 700 ℃ to 900 ℃.
4. The method for negative utilization of biomass carbon using molten salt according to claim 1, wherein the gasifying agent in the step (1) is one or more selected from the group consisting of air, steam, oxygen and carbon dioxide.
5. The method for negative utilization of biomass carbon using molten salt according to claim 4, wherein the gasifying agent in the step (1) is one or more selected from the group consisting of steam, oxygen and carbon dioxide.
6. The method for negative utilization of biomass carbon by using molten salt according to claim 1, wherein the diameter of the solid calcium-based particles in the step (2) is 0.01-1 mm.
7. The method for negative utilization of biomass carbon by using molten salt according to claim 1, wherein M in the step (2) is selected from one of lithium, sodium and potassium.
8. An apparatus for carrying out the method for negative utilization of biomass carbon using molten salt according to claim 1, it is characterized by comprising a downdraft fixed bed gasification furnace, a three-phase reforming reactor and an absorbent regeneration reactor, the top of the downdraft fixed bed gasification furnace is provided with a feed inlet which is connected with a feeding device, the lower part of the downdraft fixed bed gasification furnace is provided with a gasification agent inlet, the bottom of the downdraft fixed bed gasification furnace is provided with a grate and an air outlet, an ash outlet is arranged below the grate, the air outlet is communicated with an air distribution plate at the bottom of a three-phase reforming reactor, the lower part of the three-phase reforming reactor is provided with an absorbent circulation outlet, the upper part of the three-phase reforming reactor is provided with an absorbent circulating inlet and a gas outlet, the absorbent circulating outlet is communicated with the regeneration inlet of the absorbent regeneration reactor, and the absorbent circulating inlet is connected with the regeneration outlet of the absorbent regeneration reactor.The inside of the absorbent regeneration reactor is provided with a heater, and the top of the absorbent regeneration reactor is provided with a gas outlet; biomass enters a downdraft fixed bed gasification furnace through a feeding device and a feeding hole in sequence, the biomass is gasified under the action of a gasification agent introduced from a gasification agent inlet to obtain a gasified solid product and combustible gas containing tar, the gasified solid product is separated from the combustible gas containing the tar through a grate, the gasified solid product is discharged through an ash outlet, the combustible gas containing the tar flows out of an air outlet and enters a three-phase reforming reactor through an air distribution plate for reforming reaction, the gas after the reforming reaction flows out of the three-phase reforming reactor from a first gas outlet, a mixed absorbent after the reforming reaction enters an absorbent regeneration reactor from an absorbent circulation outlet through a regeneration inlet, and the mixed absorbent is regenerated to release CO at 1000-1200 ℃ under the action of a heater in the absorbent regeneration reactor2Regeneration of the liberated CO2And the regenerated mixed absorbent flows out of the regeneration reactor through a second gas outlet, and is recycled back to the three-phase reforming reactor from a regeneration outlet through an absorbent circulation inlet.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259835A (en) * 2011-06-20 2011-11-30 中国科学院广州能源研究所 Novel method for purifying and upgrading crude synthesis gas based on molten salt characteristics
CN107029538A (en) * 2017-03-31 2017-08-11 中国科学院广州能源研究所 It is a kind of to carry out collecting carbonic anhydride and fuse salt renovation process using fuse salt
CN109294626A (en) * 2018-12-07 2019-02-01 浙江工业大学 A kind of production process and device of gasification of biomass preparing synthetic gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259835A (en) * 2011-06-20 2011-11-30 中国科学院广州能源研究所 Novel method for purifying and upgrading crude synthesis gas based on molten salt characteristics
CN107029538A (en) * 2017-03-31 2017-08-11 中国科学院广州能源研究所 It is a kind of to carry out collecting carbonic anhydride and fuse salt renovation process using fuse salt
CN109294626A (en) * 2018-12-07 2019-02-01 浙江工业大学 A kind of production process and device of gasification of biomass preparing synthetic gas

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