CN113072981A - Chemical chain deoxidation gasification synergistic CO for functional composite oxygen carrier2Transformation method - Google Patents

Chemical chain deoxidation gasification synergistic CO for functional composite oxygen carrier2Transformation method Download PDF

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CN113072981A
CN113072981A CN202110274754.6A CN202110274754A CN113072981A CN 113072981 A CN113072981 A CN 113072981A CN 202110274754 A CN202110274754 A CN 202110274754A CN 113072981 A CN113072981 A CN 113072981A
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gasification
cao
deoxidation
biomass
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CN113072981B (en
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孙朝
陈宗
孙志强
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • C10J3/72—Other features
    • C10J3/723—Controlling or regulating the gasification process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime

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Abstract

The invention discloses a chemical chain deoxidation gasification synergistic CO (carbon monoxide) for a functional composite oxygen carrier2A method of transformation by
Figure DDA0002976152310000011
And (4) carrying out redox circulation to realize deoxygenation and gasification of the biomass. The process consists of a deoxygenation reactor and a regeneration reactor. In a deoxygenation reactor, biomass, CaO and Fe are in CO2Gasifying in atmosphere, catalyzing tar cracking by CaO, and catalyzing hydrocarbon reforming by Fe to generate biochar, light tar and high-quality synthesis gas. CaO and Fe in CO2Is oxidized into Ca under the action of2Fe2O5Entering a regeneration reactor together with the biochar; gasifying the biochar at high temperature in a regeneration reactor to remove Ca2Fe2O5Reducing the reaction product into CaO and Fe, and returning to the deoxidation reactor again. The chemical chain de-linkingOxygen gasification process by continuous conversion of oxygen carriers
Figure DDA0002976152310000012
With CO2Effective activation and dissociation of (1), reduction of oxygen content of gasification products, obtaining of H2The CO-adjustable high-quality synthesis gas realizes carbon dioxide emission reduction and biomass gradient utilization; by adjusting the disorder degree of the biochar, carbon conversion and oxygen carrier regeneration at a lower temperature are realized.

Description

Functional composite oxygen carrierChemical chain deoxygenation gasification in coordination with CO2Transformation method
Technical Field
The invention relates to a chemical chain deoxidation gasification synergistic CO (carbon monoxide) for a functional composite oxygen carrier2A conversion method belongs to the technical field of combustion chemical industry and materials.
Background
The biomass is the fourth largest energy next to coal, petroleum and natural gas, has the characteristics of wide distribution, reproducibility, low pollution and the like, and can relieve the energy and environment problems of China by reasonably developing and utilizing the biomass. The utilization of biomass includes physical conversion, thermochemical conversion, biochemical conversion and the like. Biomass gasification is an important form of high-grade utilization of biomass energy. The biomass gasification technology is that under the condition of high temperature, air, steam and the like are used as gasifying agents to convert biomass into CO and H through thermochemical reaction2And low molecular hydrocarbons and the like. The traditional non-catalytic gasification technology has the defects of low quality of synthesis gas, high tar content, carbon deposit, high oxygen content of products and the like.
The chemical chain gasification of biomass is an innovative gasification technology based on chemical chain combustion, lattice oxygen in an oxygen carrier is used for replacing a gaseous oxidant to participate in reaction, and H is obtained by controlling the proportion of the oxygen carrier, a gasifying agent and biomass2And syngas with CO as the main component. Compared with the traditional non-catalytic gasification process, the biomass chemical-looping gasification has the following potential advantages: 1) the oxygen carrier provides lattice oxygen for gasification, and compared with pure oxygen gasification, the oxygen carrier greatly saves the cost of oxygen generation; 2) compared with air gasification, NO is eliminatedxPotential generation of and dilution of syngas by air; 3) the oxygen carrier can also be used as a catalyst for tar cracking and hydrocarbon reforming, which is beneficial to reducing the tar content in the gasification product and improving the quality of the synthesis gas; 4) the synthetic gas has higher low calorific value, and the gasification efficiency is improved; 5) according to the different yield and concentration of the synthesis gas components, different chemical raw materials can be prepared.
The oxygen carrier plays an important role in the chemical chain gasification process, and in the existing research, the iron-based oxygen carrier is widely applied due to cost effectiveness and oxygen carrying capacity, but the sintering existsAnd agglomeration problems. Combining Fe with CaO can homogenize it to Ca at the atomic level2Fe2O5Thereby improving oxygen carrier performance, therefore, Ca2Fe2O5Is widely concerned as a potential high-performance oxygen carrier. The existing Ca-based2Fe2O5The biomass chemical chain gasification technology mainly comprises a Fuel Reactor (FR) and a Steam Reactor (SR), Ca2Fe2O5The oxygen carrier is subjected to reduction reaction with volatile components and fixed carbon in the biomass in FR to generate synthesis gas as a target product, and then the reduced oxygen carrier (Fe + CaO) is sent into SR and is oxidized into Ca by steam2Fe2O5And the mixture enters the FR again to be gasified, so that a chemical chain circulation is formed. The energy consumption required by the chemical chain reaction in the existing means is high, and the quality of the synthesis gas needs to be improved.
Disclosure of Invention
Aiming at the problems of high tar content and oxygen-containing CO in the gasification product in the prior biomass chemical-looping gasification technology2And H2The invention provides a functional composite oxygen carrier chemical chain deoxidation gasification cooperated with CO, and solves the problems that the O content is high and the quality of the synthesis gas is limited2The conversion method aims at improving the synergistic activation catalysis of carbon dioxide and biomass, reducing the emission of carbon dioxide, and is beneficial to improving the content and purity of synthesis gas and reducing the oxygen content of tar, and is also beneficial to realizing the cyclic preparation of a regenerative chemical chain.
Chemical chain deoxidation gasification synergistic CO for functional composite oxygen carrier2A method of transformation comprising the steps of:
step 1): deoxygenation and gasification of biomass
The mixture of the biomass, CaO and Fe is deoxidized and gasified at 700-1000 ℃ in carrier gas containing carbon dioxide to obtain the mixture containing H2Syngas of CO, and carbon-Ca2Fe2O5Mixing;
the mol ratio of CaO to Fe is 1: 1-1.1; the mass ratio of (CaO + Fe)/B (the mass ratio of the total weight of calcium oxide and iron to the biomass) is greater than 0 and less than or equal to 0.4;
in the carrier gas, the flow rate of the carbon dioxide is more than 0 and less than or equal to 80 cm/min;
step 2): regeneration of calcium ferrite oxygen carrier
Adding carbon-Ca2Fe2O5The compound is regenerated at the temperature of 800-950 ℃ to obtain CaO, Fe, CO and CO2The regeneration gas of (2);
recycling the regenerated CaO and Fe to the step 1).
The invention reports that biomass, CaO and Fe are subjected to gasification reaction in carbon dioxide atmosphere for the first time, and the gasification reaction is further based on a gasification agent (CO) in the treatment process2) Coordinated control of flow rate, temperature, and (CaO + Fe)/B mass ratio effects CO at the CaO (111)/Fe (110)/AC interface2The most stable adsorption of (1) can further reduce the adsorption energy of carbon dioxide, which is helpful for improving the gasification of biomass, increasing the yield and content of reducing atmosphere of synthesis gas, and reducing the oxygen content of tar, and is also helpful for obtaining high disordered carbon (high amorphous carbon), which can be converted unexpectedly under low temperature condition to realize low temperature regeneration of CaO-Fe, and the product can be circulated to the step 1) as a chemical chain link to realize a chemical chain process. The technical scheme of the invention has better carbon dioxide emission reduction effect, better synthesis gas quality, lower chemical chain regeneration condition and better industrial practical value.
According to the technical scheme, the biomass, CaO and Fe are subjected to gasification reaction in a carbon dioxide fluid medium, and the CO is cooperatively controlled based on the carbon dioxide flow rate, the Fe consumption and the temperature in the gasification reaction process to realize CO2The most stable adsorption of the active carbon to prepare the high-disordered carbon-Ca2Fe2O5The key to the mixture.
In step 1) of the invention, based on Fe0→Fe3+The mechanism of (2) realizes the gasification of biomass, and the processing mechanism is as follows:
biomass + CO2+Fe+CaO→Ca2Fe2O5+ carbon material + syngas + bio-tar.
In the invention, the biomass can be replaced by at least one of coal, sludge, plastic garbage and solid waste.
In the present invention, (CaO + Fe)/B means a ratio of the total mass of CaO and Fe to the mass of biomass.
In the invention, the mass ratio of (CaO + Fe)/B is 0.1-0.3: 1; more preferably 0.1 to 0.2: 1.
In the invention, step 1) is carried out in a fluidized bed;
preferably, the flow rate of the carbon dioxide in the carrier gas is 10-40 cm/min; further preferably 20 to 30 cm/min.
Preferably, in the step 1), the deoxidation gasification temperature is 850 to 950 ℃.
Preferably, in step 1), I of the amorphous carbon isD/IG0.87 to 3.25.
In the present invention, the calcium ferrite may be replaced with a metal or an oxide capable of forming a composite oxide having a spinel-type, perovskite-type, or brownmillerite-type structure.
In the invention, the step 2) is carried out in an atmosphere containing CO;
preferably, the CO atmosphere is generated by the gas generated in the step 2).
Preferably, in step 2), the regeneration temperature is 850 ℃ to 950 ℃.
The regeneration reactor in the step 2) adopts solar energy supply or industrial waste heat supply.
In the present invention, the step 2) is performed in a fixed bed or moving bed reactor.
Has the advantages that:
1. the invention reports for the first time that biomass, Fe and CaO are subjected to gasification reaction in the carbon dioxide atmosphere, and compared with the existing gasification treatment process of biomass and oxygen carrier, the invention is beneficial to obtaining better yield and quality of synthesis gas and lower oxygen content of tar. The syngas yield can be increased by 16.37% compared to a (CaO + Fe)/B mass ratio of 0.2 without CaO-Fe addition, with a CO yield increase of 69.11%. In addition, during biomass gasification, CaO + Fe → Ca is passed2Fe2O5Can realize the growth ofPartial deoxygenation of material/bio-oil;
2. based on the gasification reaction of the biomass, the Fe and the CaO in the carbon dioxide atmosphere, compared with the existing gasification treatment process of the biomass and the oxygen carrier, the invention adopts the steps of Fe + CaO + CO2→Ca2Fe2O5+ CO, has better carbon dioxide emission reduction ability. The mass ratio of (CaO + Fe)/B is 0.2, CO is less than that of the additive without CaO-Fe2The decrement is increased from 2.25 mmol/g-biomass to 8.73 mmol/g-biomass, and is improved by 288%;
3. based on the treatment process of the step 1), the combined control of the Fe dosage, the carbon dioxide flow rate and the treatment temperature can generate a synergistic effect, thereby being beneficial to the gasification of biomass, reducing the oxygen content of synthesis gas, controlling the graphitization degree and the form of the carbon material obtained by carbonization, and obtaining amorphous carbon-Ca2Fe2O5The mixture has milder reaction temperature, and is more favorable for realizing chemical chain process taking Fe-CaO as a bond. And realizing result display: when the amount of Fe added reaches the mass ratio (CaO + Fe)/B of 0.2, ID/IGUp to 3.25;
4. CaO-Fe-AC (amorphous carbon) System, CO, based on the invention2Can realize effective adsorption, activation and dissociation on the CaO/Fe/AC material. CO is obtained by density functional theory calculation2Most stable adsorption site position CaO (111)/Fe (110)/Amorphous Carbon (AC) three-phase interface, CO2The adsorption is stable at the interface and is effectively converted into CO + O, wherein O can be combined with carbon material to form CO, and the reaction energy barrier of the process is-1.87 eV and is lower than that of CO2The adsorption energy on the surfaces of Fe (110) and graphene is-1.47 eV and-0.188 eV respectively, so that the constructed CaO-Fe material is more beneficial to CO2Activation and dissociation of (2).
Based on the analysis, the method for refining the synthesis gas based on the calcium ferrite oxygen carrier chemical chain deoxidation method is simple and easy to implement, convenient to operate, high in synthesis gas quality, low in carbon product conversion temperature, suitable for industrial application and capable of obtaining high-quality raw materials or energy.
Drawings
FIG. 1 shows that chemical chain deoxidation gasification of functional composite oxygen carrier is cooperated with CO2Summary of the transformation process flow diagrams fig. 2-15 are experimental results, wherein,
FIG. 2 is a graph showing the change with time of a gasified syngas in example 1 in which the (CaO + Fe)/B mass ratio is 0.2
FIG. 3 is a Raman spectrum of biochar with gasification time in example 1
FIG. 4 biochar I of example 1D/IG(degree of disorder) according to gasification time
FIG. 5 is a graph showing changes in gasification time of gasification syngas according to example 2((CaO + Fe)/B mass ratio of 0.1)
FIG. 6 shows the change of gasification syngas with gasification time according to example 3 (gasification temperature 950 ℃ C.)
FIG. 7 shows example 4 (CO)2Flow rate of 30cm/min) change of gasification syngas with gasification time
FIG. 8 is the change of gasification syngas with gasification time of example 5 (regeneration temperature 950 ℃ C.)
FIG. 9 is a graph showing changes over time of the gasified syngas of comparative example 1 (CaO + Fe)/B mass ratio of 0
FIG. 10 is a Raman spectrum of biochar according to gasification time in comparative example 1
FIG. 11 is comparative example 1 biochar ID/IG(degree of disorder) according to gasification time
FIG. 12 influence of (CaO + Fe)/B mass ratio on syngas yield
FIG. 13(CaO + Fe)/B mass ratio of syngas CO2Influence of concentration
FIG. 14 mass ratio of (CaO + Fe)/B to CO2Influence of reduced displacement
FIG. 15 shows comparative example 2 (CO)2Flow rate of 0cm/min) change of gasification syngas with gasification time
Fig. 16 to 21 are quantum chemical calculation results, in which,
FIG. 16 adsorption energies at different adsorption sites of CaO (111)/Fe (110)/AC interface
FIG. 17 CaO (111)/Fe (110)/AC interface CO2Side view of the most stable site of adsorption
FIG. 18 CaO (111)/Fe (110)/AC interface CO2Adsorption most stable adsorption site
FIG. 19 CaO (111)/Fe (110)/AC interface CO2Adsorption transition state
FIG. 20 CaO (111)/Fe (110)/AC interface CO2Dissociation site
FIG. 21 CaO (111)/Fe (110)/AC interface CO2Relative energy of adsorption, activation and dissociation
Detailed Description
The present invention will be further described with reference to examples, comparative examples and drawings attached to the specification.
In the following cases, the biomass (code B) is pine, unless otherwise stated.
In the following case, the Ca to Fe ratio refers to a molar ratio.
Example 1: through experimental tests
1) 1.000g biomass and a mixture of CaO and Fe (0.200g, Ca: Fe ═ 1: 1; introducing into a deoxygenation reactor at a mass ratio of (CaO + Fe)/B (the mass ratio of the total mass of CaO and Fe to the biomass is 0.2), heating to 850 deg.C at a rate of 170 deg.C/min, and adding N2Is used as carrier gas with flow rate of 80cm/min, and CO is added into the carrier gas2And CO2The flow rate was 20 cm/min. The main products are biochar and synthesis gas, and contain a small amount of byproduct tar, and the relationship between the components in the reaction gas and the time is shown in figure 2.
2) After the gasification was completed, the atmosphere in the temperature rise stage was switched to 100 vol.% N2And the flow rate is 80cm/min, and the regeneration stage of the oxygen carrier is carried out. Gasifying the biochar at the high temperature of 850 ℃ to obtain CO and CO as products2While adding Ca2Fe2O5Reducing the reaction product into CaO and Fe.
The gas is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 2. When the gasification time reaches 42.5min, the total gas yield is 83.96mmol g-1Bioglass, CO yield 47.40mmol g-1·biomass，H2The yield was 18.15mmol g-1·biomass。
Raman spectrum of gasification product biochar along with gasification time and biochar ID/IGThe changes in (degree of disorder) with gasification time are shown in fig. 3 and fig. 4, respectively. Biochar ID/IGThe gasification time increased significantly, and increased from 0.87 (gasification time 0min) to 3.25 (gasification time 180 min).
Example 2:
the difference compared to example 1 is only that (CaO + Fe)/B is different during gasification.
1) Introducing 1.000g of biomass and a mixture of CaO and Fe (0.100g, Ca: Fe ═ 1:1) into a deoxygenation reactor, heating to 850 ℃ at a heating rate of 170 ℃/min, and heating with N2Is used as carrier gas with flow rate of 80cm/min, and CO is added into the carrier gas2Wherein, CO2The flow rate was 20 cm/min. The main products are biochar and synthesis gas, and contain a small amount of byproduct tar.
2) After the gasification was completed, the atmosphere in the temperature rise stage was switched to 100 vol.% N2The flow rate is 80cm/min, the temperature of the reactor is raised to 850 ℃ at the heating rate of 170 ℃/min, and the oxygen carrier regeneration stage is carried out. Gasifying biochar to obtain CO and CO2While adding Ca2Fe2O5Reducing the reaction product into CaO and Fe.
The gas produced is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 5. When the gasification time reaches 42.5min, the total gas yield is 75.38mmol g-1Bioglass, CO yield 46.01mmol g-1·biomass，H2The yield was 13.16mmol g-1Bioglass. Compared with example 1, the total gas yield is compared with CO and H2The yield is reduced.
Example 3:
the difference compared to example 1 is only the temperature difference during the gasification.
1) Introducing 1.000g of biomass and a mixture of CaO and Fe (0.200g, Ca: Fe ═ 1:1) into a deoxygenation reactor, heating to 950 ℃ at a heating rate of 170 ℃/min, and heating with N2Is used as carrier gas with flow rate of 80cm/min, and is added into carrier gasCO2Wherein, CO2The flow rate was 20 cm/min. The main products are biochar and synthesis gas, and contain a small amount of byproduct tar.
2) After the gasification was completed, the atmosphere in the temperature rise stage was switched to 100 vol.% N2The flow rate is 80cm/min, the temperature of the reactor is raised to 850 ℃ at the heating rate of 170 ℃/min, and the oxygen carrier regeneration stage is carried out. Gasifying biochar to obtain CO and CO2While adding Ca2Fe2O5Reducing the reaction product into CaO and Fe.
The gas produced is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 6. When the gasification time reaches 42.5min, the total gas yield is 82.88mmol g-1Bioglass, CO yield 58.75mmol g-1·biomass，H2The yield was 15.55mmol g-1Bioglass. Compared with example 1, the total gas yield is compared with CO and H2The yield is obviously increased, so that the gasification temperature is increased to facilitate the deoxygenation and gasification of the biomass, but the energy consumption is higher.
Example 4:
the only difference compared to example 1 is that CO is present in the gasification process2The flow rates are different.
1) Introducing 1.000g of biomass and a mixture of CaO and Fe (0.200g, Ca: Fe ═ 1:1) into a deoxygenation reactor, heating to 850 ℃ at a heating rate of 170 ℃/min, and heating with N2Is used as carrier gas with flow rate of 80cm/min, and CO is added into the carrier gas2Wherein, CO2The flow rate was 30 cm/min. The main products are biochar and synthesis gas, and contain a small amount of byproduct tar.
2) Atmosphere switching temperature rise phase 100 vol.% N2The flow rate is 80cm/min, the temperature of the reactor is raised to 850 ℃ at the heating rate of 170 ℃/min, and the oxygen carrier regeneration stage is carried out. Gasifying biochar to obtain CO and CO2While adding Ca2Fe2O5Reducing the reaction product into CaO and Fe.
Continuously collecting the generated gas in the temperature rise and gasification stage of the deoxidation reactor, and measuring the yield of each gas component and the total yield of the gas along with the timeSee fig. 7 for the results. When the gasification time reaches 42.5min, the total gas yield is 79.55mmol g-1Bioglass, CO yield 51.57mmol g-1·biomass，H2The yield was 9.00mmol g-1·biomass。
Example 5:
the difference compared to example 1 is only the temperature difference during regeneration.
1) Introducing 1.000g of biomass and a mixture of CaO and Fe (0.200g, Ca: Fe ═ 1:1) into a deoxygenation reactor, heating to 850 ℃ at a heating rate of 170 ℃/min, and heating with N2Is used as carrier gas with flow rate of 80cm/min, and CO is added into the carrier gas2Wherein, CO2The flow rate was 20 cm/min. The main products are biochar and synthesis gas, and contain a small amount of byproduct tar.
2) Atmosphere switching temperature rise phase 100 vol.% N2The flow rate is 80cm/min, the temperature of the reactor is raised to 950 ℃ at the temperature raising rate of 170 ℃/min, and the oxygen carrier regeneration stage is carried out. Gasifying biochar to obtain CO and CO2While adding Ca2Fe2O5Reducing the reaction product into CaO and Fe.
The gas produced is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 8. When the gasification time reaches 17.5min, the CO yield is 12.35mmol g-1·biomass，CO2The yield was 1.19mmol g-1·biomass。
Comparative example 1:
the only difference compared to example 1 is that no CaO and no Fe were added during gasification.
1) Introducing 1.000g of biomass into a deoxygenation reactor, heating to 850 ℃ at a heating rate of 170 ℃/min, and adding N2Is used as carrier gas with flow rate of 80cm/min, and CO is supplemented in the carrier gas2And CO2The flow rate was 20 cm/min. The main products are biochar, tar and synthesis gas.
2) Atmosphere switching temperature rise phase 100 vol.% N2The flow rate is 80cm/min, the temperature of the reactor is raised to 850 ℃ at the heating rate of 170 ℃/min, and the biochar does not react.
The gas produced is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 9. When the gasification time reaches 42.5min, the total gas yield is 65.97mmol g-1Bioglass, CO yield 34.32mmol g-1·biomass，H2The yield was 9.38mmol g-1Bioglass. Compared with example 1, the total gas yield is compared with CO and H2The yield is obviously reduced; raman spectrum of gasification product biochar along with gasification time and biochar ID/IGThe changes in (degree of disorder) with gasification time are shown in fig. 10 and fig. 11, respectively. Biochar ID/IGThe gasification time is not obviously changed and is kept about 0.93-0.83.
Gas yield, CO, comparing example 1, example 2 and comparative example 12Concentration and CO2The results of the displacement reduction are shown in fig. 12 to 14. The syngas yield of comparative example 1 was reduced by 16.37%, CO, compared to the gasification results for example 12The concentration is increased by 44.16 percent, and CO is increased2The reduction rate is reduced from 8.73 mmol/g-biomass to 2.25 mmol/g-biomass, and the high quality of the synthesis gas is seriously influenced; comparative example 1 and comparative example 1 biochar ID/IG(FIGS. 4 and 11), biochar I obtained in example 1D/IGThe change is large (0.87-3.25), and the biochar I obtained in comparative example 1 isD/IGNo significant change (0.93-0.83), the disorder degree of the biochar is difficult to regulate and control, and the disorder degree of the biochar obtained in example 1 is larger under the same gasification time (I)D/IGLarge), the conversion temperature is milder.
Comparative example 2:
the only difference compared to example 1 is that no carbon dioxide is added during the gasification.
1) Introducing 1.000g of biomass and a mixture of CaO and Fe (0.200g, Ca: Fe ═ 1:1) into a deoxygenation reactor, heating to 850 ℃ at a heating rate of 170 ℃/min, and heating with N2Is used as carrier gas, and has a flow rate of 80 cm/min. The main products are biochar, synthesis gas and a small amount of byproduct tar.
2) The atmosphere in the temperature rise stage was switched to 100vol.％N2The flow rate is 80cm/min, the temperature of the reactor is raised to 850 ℃ at the heating rate of 170 ℃/min, and the oxygen carrier regeneration stage is carried out. Gasifying biochar to obtain CO and CO2While reducing FeO to Fe.
The gas produced is continuously collected in the temperature rise and gasification stage of the deoxygenation reactor, and the change trend of the yield of each gas component and the total yield of the gas along with the time is measured, and the result is shown in figure 15. When the gasification time reaches 42.5min, the total gas yield is 41.64mmol g-1Bioglass, CO yield 19.83mmol g-1·biomass，H2The yield was 13.97mmol g-1Bioglass. Combining the results of example 1, CO2The addition of the catalyst helps the gasification of biomass, the total gas yield is improved by 101.63 percent, and the total yield of CO and H is improved2The yield is respectively improved by 139.03 percent and 29.92 percent.
The invention provides a chemical chain deoxidation gasification synergistic CO (carbon monoxide) for a functional composite oxygen carrier2The conversion method comprises using CaO-Fe as catalyst, gasifying biomass at high temperature in a deoxygenation reactor part under carbon dioxide gas flow to produce biochar, light tar and H2、CO、CO2、CH4Equal gaseous products, CaO and Fe in CO2Oxidized into Ca under the action of gasifying agent2Fe2O5Entering a regeneration reactor together with the biochar; in the regeneration reactor part, the biochar is gasified at high temperature to remove Ca2Fe2O5Reducing into CaO and Fe, returning to the deoxidation reactor, and passing the oxygen carrier
Figure BDA0002976152290000091
The continuous conversion of (a) forms a chemical cycle. Compared with the existing biomass chemical chain gasification technology, the creativity is mainly embodied as follows:
1) in the process of chemical chain deoxidation gasification of biomass, the catalytic action of a CaO-Fe system and Ca are utilized2Fe2O5Formation of (CaO + Fe + CO)2→Ca2Fe2O5+ CO) realizes the yield increase and quality improvement of the synthesis gas and reduces the oxygen content of the tar. The (CaO + Fe)/B is increased from 0 to 0.2, the yield of the synthetic gas is increased by 16.37 percent, and the CO content is increased2The concentration is reduced by 44.16 percent；
2) By mixing biomass with Fe and CaO in CO2The gasification is realized in the gasification agent, which has positive influence on the emission reduction of carbon dioxide, the ratio of (CaO + Fe)/B is increased from 0 to 0.2, and CO is generated2The decrement is increased from 2.25 mmol/g-biomass to 8.73 mmol/g-biomass, and is improved by 288%;
3) the composition of the product is adjusted by controlling the conditions of (CaO + Fe)/B, the flow rate of the gasifying agent, the temperature, the gasification time and the like, the generation of high-disorder-degree carbon is directionally regulated and controlled, and CO is realized2Effectively adsorb, activate and dissociate on the CaO/Fe/AC material. The obtained amorphous carbon can realize Ca at lower temperature2Fe2O5+ C → CaO + Fe + CO, reducing the energy consumption of the oxygen carrier oxidation reduction cycle.

Claims (9)

1. Chemical chain deoxidation gasification synergistic CO for functional composite oxygen carrier2A method of transformation, comprising the steps of:
step 1): deoxygenation and gasification of biomass
The mixture of the biomass, CaO and Fe is deoxidized and gasified at 700-1000 ℃ in carrier gas containing carbon dioxide to obtain the mixture containing H2Syngas of CO, and carbon-Ca2Fe2O5Mixing;
the mol ratio of CaO to Fe is 1: 1-1.1; the mass ratio of (CaO + Fe)/B is greater than 0 and less than or equal to 0.4;
in the carrier gas, the flow rate of the carbon dioxide is more than 0 and less than or equal to 80 cm/min;
step 2): regeneration of calcium ferrite oxygen carrier
Adding carbon-Ca2Fe2O5The compound is regenerated at the temperature of 800-950 ℃ to obtain CaO, Fe, CO and CO2The regeneration gas of (2);
recycling the regenerated CaO and Fe to the step 1).
2. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The transformation method is characterized in that in the step 1), the transformation method isThe mass ratio of CaO + Fe/B is 0.1-0.3: 1.
3. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion method is characterized in that the biomass can be replaced by at least one of coal, sludge, plastic waste and solid waste.
4. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion process, characterized in that, in step 1), it is carried out in a fluidized bed;
preferably, the flow rate of the carbon dioxide in the carrier gas is 10-40 cm/min; further preferably 20 to 30 cm/min.
5. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion method is characterized in that in the step 1), the temperature of the deoxidation gasification reaction is 850-950 ℃.
6. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion method is characterized in that in the step 1), the I of the carbon product isD/IG0.87 to 3.25.
7. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion method is characterized in that in the step 2), the conversion is carried out in an atmosphere containing CO;
preferably, the CO atmosphere is generated by the gas generated in the step 2).
8. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion method is characterized in that in the step 2), the temperature of the regeneration reaction is 850-950 ℃.
9. The functional composite oxygen carrier chemical chain deoxidation gasification synergistic CO according to claim 12The conversion process is characterized in that the step 2) is carried out in a fixed bed or moving bed reactor.
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